US 20060057496A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2006/0057496 A1 Liu et al. (43) Pub. Date: Mar. 16, 2006
(54) PHOTORESIST COMPOSITIONS (60) Provisional application No. 60/508,222, filed on Oct. COMPRISING DAMONDOD DERVATIVES 1, 2003. (75) Inventors: Shenggao Liu, Hercules, CA (US); Jeremy E. Dahl, Palo Alto, CA (US); Publication Classification Robert M. Carlson, Petaluma, CA (US) (51) Int. Cl. G03C I/76 (2006.01) Correspondence Address: BUCHANAN INGERSOLL PC (52) U.S. Cl...... 430/270.1 (INCLUDING BURNS, DOANE, SWECKER & MATHIS) POST OFFICE BOX 1404 (57) ABSTRACT ALEXANDRIA, VA 22313-1404 (US) Novel positive-working photoresist compositions are dis (73) Assignee: Chevron U.S.A. Inc., San Ramon, CA closed. The monomers of the base resin of the resist contain diamondoid-containing pendant groups higher than adaman (21) Appl. No.: 11/266,333 tane in the polymantane Series; for example, diamantane, triamantane, tetramantane, pentamantane, heXamantane, etc. (22) Filed: Nov. 4, 2005 The diamondoid-containing pendant group may have hydro Related U.S. Application Data philic-enhancing Substituents Such as a hydroxyl group, and may contain a lactone group. Advantages of the present (62) Division of application No. 10/764,407, filed on Jan. compositions include enhanced resolution, Sensitivity, and 23, 2004. adhesion to the Substrate.
105 Patent Application Publication Mar. 16, 2006 Sheet 1 of 26 US 2006/0057496 A1
Patent Application Publication Mar. 16, 2006 Sheet 2 of 26 US 2006/0057496 A1
KF (248 nm) ArF (193 nm)
.2 F (157m) EUV (13 nm)
O O
OH A. O Fo O PCH CH3
O SO. Patent Application Publication Mar. 16, 2006 Sheet 3 of 26 US 2006/0057496 A1
Triamaritane Cisza
Tetananares Diamond Lattice C2. He - 4 structures
Pentamantanes CH - 9 structures CH - 1 structure
Hexamantanes CHs - 28 structures CH-10 structures Cash - 1 structure
Heptamantanes CH - 85 structures CH-67 structures Chs - 6 structures CH-2 structures
Octamantanes Cash4 C7Haz Cash40 Ches Cash'ss
Nonamantanes Undecamantanes CH Csohlss Decamantanes '' VV Cai4248 Has C4ghs Cass2 Caoha, CH Cashso Cash42 CH48 S2 C4448 Chao 46 50 CH CH CH 42 4s 3S 4548 Cash C42h44 Cash40 C4H42 Cash's C39H40 TFIG.3 Patent Application Publication Mar. 16, 2006 Sheet 4 of 26 US 2006/0057496 A1
Step 1 Compare & Select Feedstocks
Step 2 Develop GC/MS Assay for Individual Higher Dianondoids
Step 3 Distill Feedstock to Concentrate Higher Diamondoids in Atmospheric Residuum
Step 4 (Optional) Fractionate Higher Diamondoids by High Temperature Vacuum Distillation
Step 5 (Optional) Fractions to Renove Nondiamondoids Thereby Concentrating Higher Diamondoids
Step 7 Step 6 (Optional) Step 7 Isolate Higher Diamondoid by Remove Aromatic and Polar isolate Higher Diamondoid by Multi-Column HPLC Compounds by Low-Pressure Preparative Gas
Liquid Chromatography Chromatography
Step 8 (Optional) Further Purify HPLC Fractions Using Preparative Gas Chromatography and vice versa
TFIG.4 Patent Application Publication Mar. 16, 2006 Sheet 5 of 26 US 2006/0057496 A1 TIG. 5A
Isolation of Diamondoids
Derivatization Reactions on secondary and tertiary carbons
Primary Derivatives of Diamondoids
Further Derivatizations (secondary derivatives of diamondoids)
(FIG. 5(B WUV transparency Hydrophilicity, Etch resistance polymerizability, ...
r n e o n - a sess so se - - - - - essess son ------
is a s as a as as a a was s a on a was a a sensus wou as as s so or
Mechanical properties Solubility TT modification Patent Application Publication Mar. 16, 2006 Sheet 6 of 26 US 2006/0057496 A1 (FIG. 6
FRReFreeRae D-SH -D-OH D= D-C D-COOH .
D-E--D-Br D-NH. CIRE D-CONH
D-Br D-CHO D-CN
TIG. 7
Representative Ways of Generation of Diamondoid Cations (D) D-do D-NSO - N /or SbF5 H D-X -- D -- D-OH X = Cl, F, Br H SbFs - H. D-OCOC D Patent Application Publication Mar. 16, 2006 Sheet 7 of 26 US 2006/0057496 A1 TIG. 8
Representative SN1 Reactions of Diamondoid Carbocations D-OCH D-OH D-NHCOCH, CHOH HO 1) CHCN 2) HO NH D-NH. -- D ----D-N. i. RCH=CHty- SNX D-X D-CH=CHR 1) CO 2) HO D-Air D-COOH
TIG. 9
Representative SE2 Reactions of Diamondoids
D-OH HO/HO, HCO NO D-CHO -e- --> D-NO, 3/ Nyer. D-R D-X Patent Application Publication Mar. 16, 2006 Sheet 8 of 26 US 2006/0057496 A1 FIG 10 styl-D-Br: D-(OH) e.g. n-2 BBr-Br AlBr (trace) 48%. HBf refux e-g- in Refu. V Br-BBr-AlBr D-B Br (liq.) reflux, 80 deg. C 5 -e- -- D-Br r. or reflux
Br-AlBr AlBr-Br 40 deg C 140 deg. C
D-B 4
TIG. 11
D-Cl AC/SOC -- AlCl/CC C 2 D-Cl3 T. 2. D-Cl2
hy CC r.t. Cl
D-C (C-2 D-CI+ C-3 D-Cl)
Patent Application Publication Mar. 16, 2006 Sheet 10 of 26 US 2006/0057496 A1 TIG. 14
D-(COOH) CHCN 100% BSO 1) HSO t. KOE 2) CH3CN diethylene D-(Br) ) HO glycol or D-(OH) D-(NHCOCH) -- D-(NH2)n etber (if use NaCN, then formylamino-D formed) BC gas (CECN can be also any RCN, R-alkyl, aryl, etc.) n=1,2,3, 4, ... D-(NH2)Cl
TIG. 15
NO, or HNO-Acetic acid (glacial) See C with high temp and pressure E- (140 deg. C/500 p.s.liga N.) potassium permanganate, reflux NaS 9HO D-NH2 - O -o- D-NO2 - - - D-NH2
NO 200 deg. C Patent Application Publication Mar. 16, 2006 Sheet 11 of 26 US 2006/0057496 A1 TIG. 16
C | Eus, t O "rchite o - C -e-Air -C diales.--> D-CH -dicycle G - d. CH CH -ao --65 des. C CH bel (20 des. O ch bat (20 des a dih, - H3r - HBr Hy HSO D-CH s CHCH(OH)CH H-e- CHCHCH-DCH ". SO 5-cH + CH-CHCHCHCHCH - -- Chird(CH), (mory lostners) Bf Hs Fed CH + CH, -o- -ch, l, Ode. C CH B CHOH (p) 180 deg C Hic-i-B + CHOH (excess) -e- HC--cloh p CH CH
TIG. 17
D-COOH SOCl/ether D-coc ---CHN D-COCHN,
CHN HNNHHO R’-NHN hP CH-NH (D-CONH) D-CON D-conHR D-CHCONH-CH
heat N". NOBr. R"-NH, D-NCO -r-be DNBCONHR" D-CONHNH, R"-CH or D-CO) Patent Application Publication Mar. 16, 2006 Sheet 12 of 26 US 2006/0057496 A1 TIG. 18
D-NH, co - D-NH-CHCN ---Ho D-NH-CH cooh re D-NHNH, --Pio o°- D-Nich coob NNo. acco NO
C-Socic -- D-CH,Nbso-ca-CB, D-CONH2 --lia D-CHNH N-> D-CHNHCo-Chs c-Co-CH
TIG. 19
CHOH / HC --D-po(OH), A Bri D-Br-PCl D-POCl. n D-PH, -FO, D-P(OH), PC 2 D-PCl; LiAlH HO
FIG. 20
D-SOR D-soNa D-SONRR" ns re . . ." D-SOOR D-SONR'R'" Rankyl gray, etc. R, R E. Aky, Ary, Aryanky ete Patent Application Publication Mar. 16, 2006 Sheet 13 of 26 US 2006/0057496 A1 TIG. 21
R R 2 H C C 20 b O c 2 8 28 R 9 Rs r 2 O R. R 22
24 26
R R R R R B H H H H H O C C C C C P O b C O / d R. O. R. R. d. Rs R. R.O. R. R. R. R. 9 is R.
220 222 R
C R C (H. ag (CRsR n D Patent Application Publication Mar. 16, 2006 Sheet 14 of 26 US 2006/0057496 A1 TIG. 22
Ouaternay 1.Carbon (4'C) Patent Application Publication Mar. 16, 2006 Sheet 15 of 26 US 2006/0057496 A1 TIG. 23 (, ) is E. ( ) is E. A ?h; big CHO C18HO Chris0. CHO Ohnishi's Number (O.N.) .3.0 2.75 260 250
B CH CH CH CH itsH E).O / a -(sH2 b HC O / C H2 O /d) O O O
- HOH --OH HO- HO- --OH - HOH HO- - HOH
OH
CHO CHO CHOs Cash;Os Ohnishi's Number (O.N.) 3.36 3.28 3.23 3.20 Patent Application Publication Mar. 16, 2006 Sheet 16 of 26 US 2006/0057496A1 TIG. 24
232 236
230 se: 240 A -
B
C
D Patent Application Publication Mar. 16, 2006 Sheet 17 of 26 US 2006/0057496 A1 ?FIG. 25
A Patent Application Publication Mar. 16, 2006 Sheet 18 of 26 US 2006/0057496 A1 TIG. 26
CH H2C CHo theO O os-CH
A OH B -C- H2CF O O O )- O C D Yeh,
A-B-A C B
a-e-B-C-C B --C A-C-B
; ------D-D-D-D-D; A B C s no so us s a e o wo up up or a se as a s p ap o o a an :------: D-D-D-D--A-B Patent Application Publication Mar. 16, 2006 Sheet 19 of 26 US 2006/0057496 A1 TIG. 27
O O 2-(bromomethyl)- Sr.O O Br tert-butyl acrylate -- > O O
NaOBu-t, THF, 0 to r.t N O O O O O O H 2-(bromonethyl)- O O O O tert-butyl acrylate
- - - O O O O NaOBu-t, THF g 2 E. O to t.t THF, reflux, methylazoisobutyrate or 2,2'-azobisisobutyronitrile (AIBN)
Patent Application Publication Mar. 16, 2006 Sheet 20 of 26 US 2006/0057496 A1 TIG. 28
N 8.0x10' S s SS 9 s C P / 5 5 6.0x10' 2 2 3 4. s t w C : 2 5 O 5. 4.0x10 2 C s
09 : H 2.0x1O .
O
to 0.0 - 1O 11 12 13 14 15 16 17 18 GC Retention Time (min.) Patent Application Publication Mar. 16, 2006 Sheet 21 of 26 US 2006/0057496 A1 TIG. 29
alous reas FA ess -eeeooldee eCoO r seeeee! acsoooo; sascoco i a2eeeo
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s sooo w oooo. a or as sooo L 22O sessorsecsec cornAN.A. oso so al...son so esco ---...- so eSease - casesT - Patent Application Publication Mar. 16, 2006 Sheet 22 of 26 US 2006/0057496 A1 TIG. 30
9 Ox10
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O. s Patent Application Publication Mar. 16, 2006 Sheet 24 of 26 US 2006/0057496 A1 TIG. 32
3.0x10'- 8 s s E
20x10 2 g. C ?o CC 1.x10 s H9
0.0 11 12 13 14 15 1S 17 18 19 GC Retention. Time (min.)
w N 3.0x10'
2.5x10' N N 20x10'
3C O N C 1.5x1O D O C 10x10'
5.0x10 A O.O FIA: A. Hill, 50 OO 150 2OO 2SO nz Patent Application Publication Mar. 16, 2006 Sheet 25 of 26 US 2006/0057496 A1 TIG. 334
Box1 o' U s 6.0x10 C C 40x10'
20x10
O.O 13 14 15 16 17 18 GC Retention Time (min.)
Di-alcohol
6.0x10' Monother
3 C s 2 40x10' C
20x10'
O.O 13 14 15 18 17 18 GC Time (min.) Patent Application Publication Mar. 16, 2006 Sheet 26 of 26 US 2006/0057496 A1 TIG. 34
3.2x10'
2.4x1 o'
1.6x10'
a.0x10
3. 4. 15 16 S Retention Time (min.) S 2.5x10'
2.Ox10
10x1O S 5.0x10' s O.D R8 E. s SO 2O BC 240 US 2006/0057496 A1 Mar. 16, 2006
PHOTORESIST COMPOSITIONS COMPRISING which after development provides a relief image that can be DAMONDOD DERVATIVES used to Selectively process the underlying Substrate. 0008. In general, a photoresist composition comprises at REFERENCE TO RELATED APPLICATIONS least a resin binder and a photoactive agent. The “chemically 0001. The present application claims the benefit of U.S. amplified” resists in use today were developed for the Provisional Patent Application No. 60/508,222 filed Oct. 1, formation of Sub-micron images and other high performance 2003. U.S. Provisional Patent Application No. 60/508,222 is applications. They may be either positive or negative acting. hereby incorporated by reference in its entirety. In the case of a positive acting resist, the regions that are exposed to the radiation become more Soluble in the devel BACKGROUND OF THE INVENTION oper, while those areas that are not exposed remain com paratively leSS Soluble in the developer. Cationic initiators 0002) 1. Field of the Invention are used to induce cleavage of certain “blocking groups” pendant from the photoresist binder resin, or cleavage of 0.003 Embodiments of the present invention are directed certain groups that comprise a photoresist binder backbone. in general toward high performance photoresist composi Upon cleavage of the blocking group through exposure of a tions used in conjunction with eXimer laser and electron layer of photoresist to light, a base Soluble functional group beam lithography Sources. Specifically, the photoresist com is formed, Such as a carboxylic acid or an imide, which positions of the present invention include diamondoid results in a different solubility in the developer for the derivatives having polymerizable and hydrophilic-enhanc exposed and unexposed regions of the resist layer. ing functionalities. The diamondoids of the present inven tion include lower diamondoids Such as adamantane, dia 0009. As taught by J. D. Plummer et al., in “Silicon VLSI mantane, and triamantane, as well as the diamondoids Technology” (Prentice Hall, Upper Saddle River, N.J., tetramantane, pentamantanes, and higher compounds. 2000), pp. 221-226, deep ultraviolet (DUV) resists in use today are not modified novolac resists. Deep ultraViolet 0004 2. State of the Art (DUV) photoresist materials in use today are based on 0005 Increasing demands for devices with higher circuit chemistry that makes use of a phenomenon called “chemical densities have led to the use of Shorter wavelength light amplification.” Conventional resist materials that were Sources in optical lithography. KrF (krypton fluoride) exci designed to operate at 365 nm and 248 nm achieved quan mer laser lithography operating at a wavelength of 248 nm tum efficiencies of about 0.3, meaning that about 30 percent has has been used for the production of devices having of the incoming photons interacted with the photoactive feature sizes ranging from 0.25 to 0.13 microns. Rapid compound to expose the resist. advances in the miniaturization of microelectronic devices, 0010 DUV resists, according to Plummer, work on a and demands for devices with increasingly greater circuit different principle that is illustrated in FIG. 1. Referring to densities, are requiring the development of new, imageable FIG. 1, incoming photons react with a photo-acid generator polymeric photoresist materials to be used with ArF (argon (PAG) 101, creating an acid molecule 102. Acid molecules fluoride) excimer laser lithography at 193 nm, and there is 102 act as catalysts during a Subsequent resistant bake to a need on the horizon for resist materials which can operate change the properties of the resist in the exposed region. The in the extreme ultraViolet and Soft X-ray regim. According to photo-acid generator 101 initiates a chemical reaction that The National Technology Roadmap for Semiconductors, makes the resist Soluble in a developer in a Subsequent (Semiconductor Industry ASSociation, San Jose, Calif., developing Step that occurs after exposure to the radiation. 1997), the next most likely candidate is an F source oper The reactions are catalytic and the acid molecule 102 is ating at 157 nm. regenerated after each chemical reaction and may therefore 0006 Conventional g-line (436 nm) and i-line (365 nm) participate in tens or even hundreds of further reactions. This photoresists are well-balanced in terms of high-resolution, is what allows the overall quantum efficiency in a chemically high Sensitivity, and good dry etch resistance, but they amplified resist to be much larger than 1, and is responsible typically comprise a novolac base resin and a diazonaph for improving the Sensitivity of a chemically amplified resist thoquinone PAC (photoactive compound), both of which from the previous values of about 100 m) cm for conven contain a phenolic moiety that absorbs light having wave tional diazonaphthoguinones to the current values of about lengths below about 365 nm. Thus, the phenolic based 20-40 for the new chemically amplified the ultraviolet resists cannot be used in these shorter wavelengths regimes, photoresists. Such as those found in Arf lithography, because they are 0011. The principle of a chemically amplified photoresist completely opaque at 193 nm. The incident radiation cannot is illustrated in FIG. 1. Referring again to FIG. 1, photo penetrate through the full thickness of the resist. This is a resists of the present intention included in general a photo Significant issue at 248 nm (KrF), which is the wavelength acid generator 101 and a blocked or protected polymer 103 used for 0.25 micron and 0.18 micron generation devices. which is insoluble in the developer because of attached 0007 Photoresists are materials used to transfer an image molecules 104 (labeled additionally “INSOL” in FIG. 1). onto a substrate. A layer of the photoresist (or “resist”) is Incident deep ultraViolet photons interact with the photo formed on a Substrate, and then exposed through a mask to acid generator 101 to create an acid molecule 102. The a Source of radiation. The mask has Some regions that are spatial pattern of the acid molecules 102 within the resist opaque, and Some regions that are transparent to the radia create a “stored,” or latent image of the mask pattern. After tion. The portions of the photoresist that are exposed to the exposure, the Substrate undergoing processing is baked at a radiation undergo a chemical transformation Such that the temperature of about 120 degrees C. in a process called post pattern of the mask is transferred to the photoresist layer, exposure bake (PEB). The heat from the post exposure bake US 2006/0057496 A1 Mar. 16, 2006
provides the energy needed for the reaction between the acid hydrocarbon Streams Such as natural gas Streams. A number molecules 102 and the insoluble pendant groups 104 where of diamantane derivatives have been reported in the litera the reaction is to take place. The heat from the post exposure ture including a variety of mono and poly halides, mono bake provides the energy needed for the reaction between and dihydroxy materials, mono- and dicarboxylic acid acid molecules 102 and the insoluble pendant groups 104 derivatives, mono- and dialkynyls, and mono- and diamines. attached to main polymer chain 103; the heat from the post In addition, there are a number of diamantane-containing exposure bake also provides diffusion mobility for the acid polymers in the literature but generally these materials molecules 102 to seek out unreacted pendant groups 104, the appear to link the diamantane into the polymer through two essence of the catalytic nature of this reaction. or more linkS Such that the diamantane forms an integral part 0012. During the post exposure bake, the insoluble pen of the polymer backbone. dant groups 104 are either converted to soluble pendant 0018 We now desire to provide a family of derivatives of groups 105, or cleaved from the polymer chain 103. In either diamantane that can form polymers having pendant diaman case, the insoluble, blocked polymer is converted to an tyl groups. In addition, these derivative can contain addi unblocked polymer as Soluble in an aqueous alkaline devel tional functionality to impart desirable properties to the oper. polymers they form. 0013 The polymers that comprise the chain 103 may SUMMARY OF THE INVENTION comprise Such polymers as polyamides, polyimides, poly esters, and polycarbonates Since these are easily processed, 0019 Embodiments of the present invention are directed mechanically strong, and thermally stable, and thus have to positive working photoresist compositions useable at become important materials in the microelectronics industry. lithography wavelengths less than about 200 nm, Such as the Introduction of polycyclic hydrocarbon Substituents, includ 193 nm wavelength from an ArF eximer laser, a 157 nm F. ing alicyclic rings and other caged hydrocarbons, have been light Source, or e-beam excitation. The base resins of the shown to impart greater Solubility and enhanced rigidity, present resist compositions contain acid-cleavable, pendant improving the mechanical and thermal properties of the diamondoid groups that are generally higher in the poly resulting polymers. Previous studies have involved the intro mantane Series than adamantane. The diamondoid pendant duction of adamantyl groups into 193 nm resists, but to the groups have Substituents that increase the hydrophilic nature applicant's knowledge, there have been no previous of the diamondoids, thereby rendering them more Soluble in attempts to incorporate any diamondoid compound higher an alkali developer, and consequently enhancing their ability than adamantane into the base resin Structure. These com to resolve fine feature sizes. position may incorporate lower diamondoids Such as dia 0020 Embodiments of the present invention specifically mantane and/or triamantane into the resist Structure, or they include polymerizable diamantyl monomers having the for may include diamondoids Such as tetramantane and higher. mula Pg-D-(R), wherein D is a diamantyl nucleus, Pg is a polymerizable group covalently bonded to a carbon of the 0.014. In many instances, the use of photoacid generators diamantyl nucleus; n is an integer ranging from 1 to 6, that produce weaker photoacids and resists compositions inclusive; at least one of the RS is a hydrophilic-enhancing that require lower post exposure bake (PEB) temperatures, moiety; and each of the remaining R's is independently Such as 110° C. or less, would represent a significant Selected from the group consisting of hydrogen and a advantage. For example, if the desired deprotection chem hydrophilic-enhancing moiety. The hydrophilic-enhancing istry could be carried out with a weaker acid, a wider range moietyies of these diamantyl monomerS may be Selected of photoacid generators could potentially be employed. from the group consisting of a hydroxyl group -OH, a Moreover, the industry continually SeekS use of lowered post carboxylic group -COOH, an alkoxy group -OCH or exposure bake temperatures because of uniformity consid -OCH, a keto group -C(O), and -OC(O)-OCH or erations. -OC(O)-OCHs. 0.015 Thus, it would be advantageous to have new pho 0021. Other embodiments of the present invention pro toresist compositions, particularly positive acting photore vide for triamantyl monomers having polymerizable groups sist compositions, that may be effectively imaged in the and hydrophilic-enhancing moities Similar to those for dia Sub-200 nm wavelength region, such as 193 nm and 157 nm. mantyl monomers discussed above, as well as diamondoid It is also desirable to provide photoresist compositions that containing monomers with polymerizable groupS and hydro employ photoacid generators. philic-enhancing moities, wherein the diamondoid portion 0016 Adamantane, the smallest member of the family of of the diamondoid-containig monomer is Selected from the diamondoid compounds, is a highly condensed, exception group consisting of tetramantane, pentamantane, heXaman ally stable hydrocarbon compound. Adamantane and a range tane, heptamantane, octamantane, nonamantane, decaman of adamantyl derivatives have been commercially available tane, and undecamantane. for years. This has made adamantane a regular Substituent in 0022. Other embodiments of the present invention pro a wide variety of families of chemical Structures when a vide for methods of forming a layer of patterned photoresist large, stable, bulky hydrocarbon moiety is desired. Adaman on the Surface of a Substrate, the method comprising the tyl groups are found in polymers and are currently employed Steps of as constituents of positive photoresist materials. 0023 a) depositing on the surface of the substrate a 0017 Diamantane is also a highly condensed hydrocar layer comprising the above mentionned diamantyl, bon compound. It is made up of two face-fused adamantane triamantyl, and higher diamondoid containing mono units. It can be Synthesized but also occurs naturally in merS having polymerizable groups and hydrophilic petroleum and can be isolated from various deep well enhancing moieties, US 2006/0057496 A1 Mar. 16, 2006
0024 b) polymerizing the deposited monomers to operates, taken from J. D. Plummer et al., in “Silicon VLSI yield a polymerized layer comprising a photo-labile Technology” (Prentice Hall, Upper Saddle River, N.J., polymer on the Surface of the Substrate; and 2000), pp. 221-226; 0025 c) exposing selected regions of the polymerized 0038 FIG. 2 illustrates an exemplary photoresist that has layer to an electromagnetic beam, thereby modifying been used for KrF (248 nm) lithography, and an exemplary the photo-labile polymer in those regions exposed to photoresist that has been used for ArF (193 nm); the electromagnetic beam to yield a Selectively modi fied layer. 0039 FIG. 3 illustrates the relationship of a diamondoid to the diamond crystal lattice, and enumerates by Stoichio 0026. In another embodiment, the base resin of the resist metric formula many of the diamondoids available; may be represented by the general formula: 0040 FIG. 4 shows an exemplary process flow for iso lating diamondoids from petroleum; R1 R1 R1 0041 FIG. 5A is a flow chart that illustrates how dia H2 H2 H2 mondoids may be derivatized with hydrophilic-enhancing C C C groupS and polymerizable groups to form feed monomers, Pi/ OM, O/ which may then be polymerized to form the base resin of the resist; the base resin is then mixed with a Solvent, photoacid R2 O R3 R2 O R3 R3 generator, and other additives to produce the fully formu lated resist; 0042 FIG. 5B is a schematic showing how chemistry and processing of diamondoids into derivatized diamon doids contribute to photoresist properties, 0027 wherein R is selected from the group consisting 0043 FIGS. 6-20 illustrate exemplary pathways for of-H and -CH; derivatizing diamondoids, 0028 R is selected from the group consisting of -H, 0044 FIGS. 21A-B illustrate exemplary base resins of an alkyl group having from 1 to 4 carbon atoms, and an the present invention, wherein the base resin contains a alkoxy group having from 1 to 4 carbon atoms, diamondoid pendant group higher in the polymantane Series 0029) R is -H, or a hydrophilic-enhancing moiety than adamantane (although they may contain adamantane as Selected from the group consisting of a hydroxyl group well); -OH, a keto group, carboxylic acid group -COOH, 004.5 FIGS. 21C-D illustrate exemplary non-diamon and alkoxy group -OR, and -OC(O)OR; doid, lactone containing pendant groups; 0030 R is -CH or -CHs; 0046 FIGS. 22A-E gives nomenclature for the present Structural formulas, illustrating how the hydrophilic-enhanc 0.031) a is 0.25 to 0.75; ing and polymerizable Substituents on the diamondoids 0032) b+c=1-a; higher than adamantane have a variety of attachment points; 0033 c is greater than Zero; and 0047 FIGS. 23A-B illustrate Ohnishi parameter calcula tions for base resin repeat units having adamantane, dia 0034 P, is a non-diamondoid, acid-cleavable pendant mantane, triamantane, and iso-tetramantane pendant groups, grOup. and for the same pendant groups with 1, 2, 3, and 4 hydroxyl groups, respectively, 0035. According to other embodiments of the present invention, the diamondoid pendant groups of the base resin 0048 FIG. 24A-D shows exemplary diamondoid-con may contain lactone groups, and they may be linked to the taining monomers with multiple acid-labile sites, main polymer chain by more than one ester linking group, thereby providing multiple sites on which the photo-gener 0049 FIGS. 25A-B illustrate exemplary lactone-contain ated acid can react. This has advantages of allowing either ing pendant groups, wherein the lactone group may be part weaker acids, lower post exposure bake temperatures, and a of either the diamondoid-containing pendant group, or the greater variety of photo-acid generators from which to non-diamondoid containing pendant group; choose. The diamondoid pendant groups may contain hetero 0050 FIG. 26 illustrates an exemplary block co-polymer atoms in addition to the oxygen atom of a lactone group. The of the present invention; hetero atoms may be selected from the group of O, N, B, S, and/or P. Block co-polymers are also contemplated. 0051 FIG. 27 illustrates a synthetic pathway for produc ing a polymer containing iso-tetramantane pendant groups; BRIEF DESCRIPTION OF THE DRAWINGS 0.052 FIG. 28 shows the total ion chromatogram (TIC) 0036) This invention will be further described with ref of the resulting hydroxylation reaction mixture (10-18 min.); erence being made to the accompanying drawings in which: 0053 FIG. 29 shows the TIC of the separated di-hy 0037 FIG. 1 is a schematic diagram illustrating the droxylated diamantane with its corresponding mass Spec manner in which a positive, chemically amplified resist trum, US 2006/0057496 A1 Mar. 16, 2006
0054 FIG. 30 shows the TIC of the separated tri-hy components, to any and/or all Substituted and unsubstituted droxylated diamantane isomers with a mass spectrum of an decamantane components, to any and/or all Substituted and isomer; unsubstituted undecamantane components, as well as mix 0.055 FIG. 31 shows a process to separate and purify the tures of the above and isomers and Stereoisomers of tetra tri-hydroxylated diamantanes from the hydroxylation reac mantane, pentamantane, heXamantane, heptamantane, octa tion mixture: Step 1: Water extraction; Step 2: first flash mantane, nonamantane, decamantane, and undecamantane. column chromatography; Step 3: Second flash column chro 0063 Adamantane chemistry has been reviewed by Fort, matography. In one embodiment of the present invention, Jr. et al. in "Adamantane: Consequences of the Diamondoid Step 2 may be eliminated. Structure,” Chem. Rev. vol. 64, pp. 277-300 (1964). Ada 0056 FIG. 32 shows the TIC of the precipitated solids mantane is the Smallest member of the diamondoid Series from the hydroxylation reaction, and the mass spectrum at and may be thought of as a single cage crystalline Subunit. 17.27 minutes identifying the tetra-hydroxylated diaman Diamantane contains two Subunits, triamantane three, tetra taneS, mantane four, and So on. While there is only one isomeric form of adamantane, diamantane, and triamantane, there are 0057 FIG. 33 shows the TIC of the esterification reac four different isomers of tetramantane (two of which repre tion mixtures (A from example 10 and B from example 11) sent an enantiomeric pair), i.e., four different possible ways between 13 and 18 minutes; and of arranging the four adamantane Subunits. The number of 0.058 FIG. 34 shows the TIC of the separated mono possible isomers increases non-linearly with each higher hydroxyl diamantane methacrylate isomers with a mass member of the diamondoid Series, pentamantane, heXaman Spectrum of one of the isomer. tane, heptamantane, octamantane, nonamantane, decaman tane, etc. DETAILED DESCRIPTION OF THE 0064. Adamantane, which is commercially available, has INVENTION been studied extensively. The studies have been directed 0059 Embodiments of the present invention include dia toward a number of areas, Such as thermodynamic Stability, mondoids as pendant groups of the base resin of a positive functionalization, and the properties of adamantane-contain photoresist composition. The present disclosure will be ing materials. For instance, the following patents discuss organized in the following manner: first, the term diamon materials comprising adamantane Subunits: U.S. Pat. No. doids will be defined, followed by a discussion of isolation 3,457,318 teaches the preparation of polymers from alkenyl methods of diamondoids from petroleum feedstocks, the adamantanes; U.S. Pat. No. 3,832,332 teaches a polyamide derivatization of those isolated diamondoids, and then poly polymer forms from alkyladamantane diamine; U.S. Pat. merization of the derivatized diamondoids into photoresist No. 5,017,734 discusses the formation of thermally stable base resins. resins from adamantane derivatives; and U.S. Pat. No. 6,235,851 reports the synthesis and polymerization of a Definition of Diamondoids variety of adamantane derivatives. 0060. The term “diamondoids” refers to substituted and 0065. In contrast, the diamondoids, have received com unsubstituted caged compounds of the adamantane Series paratively little attention in the scientific literature. McKer including adamantane, diamantane, triamantane, tetraman vay et al. have reported the Synthesis of anti-tetramantane in tane, pentamantane, heXamantane, heptamantane, octaman low yields using a laborious, multistep process in "Synthetic tane, nonamantane, decamantane, undecamantane, and the Approaches to Large Diamondoid Hydrocarbons.” Tetrahe like, including all isomers and Stereoisomers thereof. The dron, vol. 36, pp. 971-992 (1980). To the inventor's knowl compounds have a "diamondoid' topology, which means edge, this is the only diamondoid that has been Synthesized their carbon atom arrangement is Superimposable on a to date. Lin et al. have Suggested the existence of, but did not fragment of an FCC diamond lattice. Substituted diamon isolate, tetramantane, pentamantane, and heXamantane in doids comprise from 1 to 10 and preferably 1 to 4 indepen deep petroleum reservoirs in light of mass spectroscopic dently-Selected alkyl Substituents. Diamondoids include studies, reported in “Natural Occurrence of Tetramantane “lower diamondoids' and "diamondoids,' as these terms are (C22H2s), Pentamantane (C2H52) and Hexamantane defined herein, as well as mixtures of any combination of (CoH) in a Deep Petroleum Reservoir.” Fuel, vol. 74(10), lower and diamondoids. pp. 1512-1521 (1995). The possible presence of tetraman 0061 The term “lower diamondoids' refers to adaman tane and pentamantane in pot material after a distillation of tane, diamantane and triamantane and any and/or all unsub a diamondoid-containing feedstock has been discussed by Stituted and Substituted derivatives of adamantane, diaman Chen et al. in U.S. Pat. No. 5,414,189. tane and triamantane. These lower diamondoid components 0066. The four tetramantane structures are iso-tetraman show no isomers or chirality and are readily Synthesized, tane 1(2), anti-tetramantane 121 and two enantiomers of distinguishing them from "diamondoids.” skew-tetramantane 123), with the bracketed nomenclature 0062) The term “diamondoids' refers to any and/or all for these diamondoids in accordance with a convention Substituted and unsubstituted tetramantane components, to established by Balaban et al. in “Systematic Classification any and/or all Substituted and unsubstituted pentamantane and Nomenclature of Diamond Hydrocarbons-I,” Tetrahe components, to any and/or all Substituted and unsubstituted dron vol. 34, pp. 3599-3606 (1978). All four tetramantanes heXamantane components, to any and/or all Substituted and have the formula C2H2s (molecular weight 292). There are unsubstituted heptamantane components, to any and/or all ten possible pentamantanes, nine having the molecular for Substituted and unsubstituted octamantane components, to mula CH-2 (molecular weight 344) and among these nine, any and/or all Substituted and unsubstituted nonamantane there are three pairs of enantiomerS represented generally by US 2006/0057496 A1 Mar. 16, 2006
12(1)3), 1234), 1213 with the nine enantiomeric penta 0074 These feedstocks contain large proportions of mantanes represented by 12(3)4), 1(2.3)4), 1212). There lower diamondoids (often as much as about two thirds) and also exists a pentamantane 1231 represented by the lower but significant amounts of diamondoids (often as molecular formula C5Ho (molecular weight 330). much as about 0.3 to 0.5 percent by weight). The processing of Such feedstocks to remove non-diamondoids and to 0067 Hexamantanes exist in thirty-nine possible struc Separate higher and lower diamondoids (if desired) can be tures with twenty eight having the molecular formula CHs. carried out using, by way of example only, Size Separation (molecular weight 396) and of these, six are symmetrical; techniques Such as membranes, molecular Sieves, etc., ten heXamantanes have the molecular formula CoH evaporation and thermal Separators either under normal or (molecular weight 382) and the remaining hexamantane reduced pressures, extractors, electroStatic Separators, crys 12312 has the molecular formula CH-so (molecular tallization, chromatography, well head Separators, and the weight 342). like. 0068 Heptamantanes are postulated to exist in 160 pos 0075) A preferred separation method typically includes sible structures with 85 having the molecular formula CH distillation of the feedstock. This can remove low-boiling, (molecular weight 448) and of these, Seven are achiral, non-diamondoid components. It can also remove or Separate having no enantiomers. Of the remaining heptamantanes 67 out lower and diamondoid components having a boiling have the molecular formula CHs (molecular weight 434), point less than that of the diamondoid(s) selected for isola Six have the molecular formula CH3 (molecular weight tion. In either instance, the lower cuts will be enriched in 420) and the remaining two have the molecular formula lower diamondoids and low boiling point non-diamondoid C.H. (molecular weight 394). materials. Distillation can be operated to provide Several cuts in the temperature range of interest to provide the initial 0069 Octamantanes possess eight of the adamantane isolation of the identified diamondoid. The cuts, which are subunits and exist with five different molecular weights. enriched in diamondoids or the diamondoid of interest, are Among the octamantanes, 18 have the molecular formula retained and may require further purification. Other methods CHs (molecular weight 446). Octamantanes also have the for the removal of contaminants and further purification of molecular formula CH (molecular weight 500); C7H2 an enriched diamondoid fraction can additionally include the (molecular weight 486); C-Ho (molecular weight 472), following nonlimiting examples: Size Separation techniques, and C.H. (molecular weight 432). evaporation either under normal or reduced pressure, Sub 0070. Nonamantanes exist within six families of different limation, crystallization, chromatography, well head sepa molecular weights having the following molecular formulas: rators, flash distillation, fixed and fluidbed reactors, reduced CHAs (molecular weight 552), C.H. (molecular weight preSSure, and the like. 538), CoH (molecular weight 524, C.H. (molecular 0076. The removal of non-diamondoids may also include weight 498), C.H. (molecular weight 484) and CH a pyrolysis Step either prior or Subsequent to distillation. (molecular weight 444). Pyrolysis is an effective method to remove hydrocarbon 0071 Decamantane exists within families of seven dif aceous, non-diamondoid components from the feedstock. It ferent molecular weights. Among the decamantanes, there is is effected by heating the feedstock under vacuum condi a single decamantane having the molecular formula CH tions, or in an inert atmosphere, to a temperature of at least (molecular weight 456) which is structurally compact in about 390 C., and most preferably to a temperature in the relation to the other decamantanes. The other decamantane range of about 410 to 450° C. Pyrolysis is continued for a families have the molecular formulas: CHs (molecular Sufficient length of time, and at a Sufficiently high tempera weight 604); CHso (molecular weight 590); C.His ture, to thermally degrade at least about 10 percent by (molecular weight 576); CH (molecular weight 550); weight of the non-diamondoid components that were in the C.H. (molecular weight 536); and Casho (molecular feed material prior to pyrolysis. More preferably at least weight 496). about 50 percent by weight, and even more preferably at least 90 percent by weight of the non-diamondoids are 0.072 Undecamantane exists within families of eight dif thermally degraded. ferent molecular weights. Among the undecamantanes there are two undecamantanes having the molecular formula 0077. While pyrolysis is preferred in one embodiment, it C.H. (molecular weight 508) which are structurally com is not always necessary to facilitate the recovery, isolation or pact in relation to the other undecamantanes. The other purification of diamondoids. Other Separation methods may undecamantane families have the molecular formulas C. He allow for the concentration of diamondoids to be sufficiently (molecular weight 534); CH (molecular weight 548); high given certain feedstockS Such that direct purification CHs (molecular weight 588), C.H.so (molecular weight methods Such as chromatography including preparative gas 602); CHs (molecular weight 628); CoH (molecular chromatography and high performance liquid chromatogra weight 642); and CsoHs (molecular weight 656). phy, crystallization, fractional Sublimation may be used to isolate diamondoids. Isolation of Diamondoids from Petroleum Feedstocks 0078 Even after distillation or pyrolysis/distillation, fur 0.073 Feedstocks that contain recoverable amounts of ther purification of the material may be desired to provide diamondoids include, for example, natural gas condensates Selected diamondoids for use in the compositions employed and refinery Streams resulting from cracking, distillation, in this invention. Such purification techniques include chro coking processes, and the like. Particularly preferred feed matography, crystallization, thermal diffusion techniques, stocks originate from the Norphlet Formation in the Gulf of Zone refining, progressive recrystallization, Size Separation, Mexico and the LeDuc Formation in Canada. and the like. For instance, in one process, the recovered US 2006/0057496 A1 Mar. 16, 2006 feedstock is Subjected to the following additional proce mondoid by one or more Subsequent reaction Steps. These dures: 1) gravity column chromatography using silver nitrate materials are Sometimes referred to herein as "Secondary impregnated Silica gel; 2) two-column preparative capillary functionalized diamondoids.” It will be appreciated that in gas chromatography to isolate diamondoids; 3) crystalliza Some cases one primary functionalized diamondoid may be tion to provide crystals of the highly concentrated diamon conveniently formed by conversion of another primary doids. material. For example, a poly-bromo material can be formed 0079 An alternative process is to use single or multiple either by Single Step bromination or by Several repeated column liquid chromatography, including high performance brominations. Similarly, a hydroxyl diamondoid can be liquid chromatography, to isolate the diamondoids of inter formed directly from a diamondoid in one Step or can be est. As above, multiple columns with different selectivities prepared by reaction of a bromo-diamondoid, a diamondoid may be used. Further processing using these methods allow oxide or the like. Notwithstanding this, to avoid confusion, for more refined Separations which can lead to a Substan the primary materials will not be included here in the tially pure component. representative Secondary materials. They will, however, be depicted in various figures showing reactions for forming 0080 Detailed methods for processing feedstocks to primary and Secondary materials to depict both routes to obtain diamondoid compositions are set forth in U.S. Pro them. visional Patent Application No. 60/262,842 filed Jan. 19, 2001; U.S. Provisional Patent Application No. 60/300,148 0085. The functionalized groups available for synthesis filed Jun. 21, 2001; and U.S. Provisional Patent Application of Secondary functionalized diamondoids can be Selected No. 60/307,063 filed Jul. 20, 2001, incorporated by refer from a wide range of groups including chloro, bromo, ence herein in their entirety. hydroxides, etc. Thus, the following types of Secondary materials are merely representatives. Derivatization of Diamondoids 0086 Representative secondary functionalized diamon 0081. According to the present embodiments, diamon doid functional groups include fluoro, iodo, thio, Sulfonyl doid pendant groups are derivatized with at least one func halide, Sulfonates, alkyl, haloalkyl, alkoxyl, haloalkenyl, tional group to allow attachment to the base polymer chain. alkynyl, haloalkynyl, hydroxyalkyl, heteroaryl, alkylthio, Preferably these derivatives have the following Formula I: alkoxy, aminoalkyl, aminoalkoxy, aryl, heterocycloalkoxy, cycloalkyloxy, aryloxy, and heteroaryloxy. 0087. Other functional groups that can be present in Secondary functionalized diamondoids are represented by the formula -C(O)Z wherein Z is hydrogen, alkyl, halo, haloalkyl, halothio, amino, monoSubstituted amino, disub Stituted amino, cycloalkyl, aryl, heteroaryl, heterocyclic; by -COZ wherein Z is as defined previously; by -R'COZ wherein D is a diamondoid nucleus; and, R., R. R. R", R and -RCOZ wherein R is alkylene, aminoalkylene, or and R are each independently selected from a group con haloalkylene and Z is as defined previously; by -NH2, Sisting of hydrogen and covalently bonded functional -NHR', -NR'R", and -N'R"R" R" wherein R', R", and groups, provided that there is at least one functional group. R" are independently alkyl, amino, thio, thioalkyl, het More preferably the functionalized diamondoids contain eroalkyl, aryl, or heteroaryl; by-RNHCOR wherein R is -CH, -OCH, -NHCH, -CHCH, -OCHCH and either one or two functional groups. R’ is alkyl, aryl, heteroaryl, aralkyl, or heteroaralkly; and by 0082 In one aspect, as described in U.S. Ser. No. 10/046, -R''CONHR' wherein R' is selected from -CH, 486, in the functionalized diamondoids represented by For - OCH, -NHCH, -CHCH, and —OCHCH, and mula I, R., R. R. R", R and R are preferably indepen R is Selected from alkyl, aryl, heteroaryl, aralkyl, and dently Selected from a group of moieties consisting of -H, heteroaralkyl. F, -Cl, -Br, -, -OH, -SH, -NH, -NHCOCH, -NHCHO, -COH, -COR', -COCl, -CHO, 0088. In a further aspect, one or more of the functional -CHOH, =O, -NO, -CH=CH, -C=CH and groups on the functionalized diamondoids may be of the -CHs; where R' is alkyl (preferably ethyl) provided that formulae: R,R, R3, R, R and Rare not all hydrogen. Typically one or two of R'-R are nonhydrogen moieties and the remaining R’s are hydrogens. X 1'''2'-RCH 12 V N 0.083. Some functionalized diamondoids can be prepared y H.), and o N from diamondoid in a Single reaction Step. These materials X X Y are referred to herein as “primary functionalized diamon Y R14 doids” and include, for example, diamondoids of Formula I M wherein the functionalizing groups are halogens, Such as -bromos and -chloros, -oxides, -hydroxyls and -nitroS as ---,R13 R15 well as other derivatives formed in one reaction from a diamondoid. 0084. In another aspect, the functionalized diamondoids wherein n is 2 or 3; X is -O-, -S-, or -C(O)-; Y is are materials prepared from a primary functionalized dia =O or =S; and R', R', R', and R' are independently US 2006/0057496 A1 Mar. 16, 2006 hydrogen, alkyl, heteroalkyl, aryl or heteroaryl; =N-Z", wherein Z" is hydrogen, amino, hydroxyl, alkyl, -continued R28 R29 R30
O S
N-R31 (CH2) cyano, cyanoalkyl, cyanoaryl, or cyanoalkylamino. 0089. In a further embodiment, one or more of the functional groups on the functionalized diamondoid is -NHR', - NR'R", - N'R"R" R", or -NHO" wherein R', R", and R" independently are hydrogen, aryl; heteroaryl with up to 7 ring members, alkyl, alkenyl; or alkynyl, wherein the alkyl, alkenyl and a kynyl residues can be branched, unbranched or cyclized and optionally Substituted wherein R. R. R. R', R, R are independently with halogen, aryl or heteroaryl with up to 7 ring members, hydrogen or alkyl, and n and m are independently from 2 to or R' and R" together with the nitrogen atom form a 20; heterocyclic group with up to 7 ring members. Q" is thio, thioalkyl, amino, monoSubstituted amino, disubstituted amino, or trisubstituted amino with an appropriate counte 28 29 rion Such as halogen, hydroxide, Sulfate, nitrate, phosphate or other anion. 0090. In still a further embodiment, the functional group R34 R35 on the functionalized diamondoid is -COOR wherein R' R28 R29 R30 is alkyl, aryl, or aralkyl, -COR'', wherein R'' is alkyl, aryl, or heteroalkyl, -NHNHO,-R'NHCOR' wherein R is absent or selected from alkyl, aryl, or aralkyl, R' is R34 R35 R36 hydrogen, alkyl, -N, aryl, amino, or -NHR' wherein R is hydrogen, -SO-aryl, -SO-alkyl, or -SO-aralkyl, R34 - R31 -CONHR wherein R is hydrogen, alkyl, and aralkyl; —CSNHR'" wherein R is as defined above; and -NR’— (CH2) R37 (CH), NR'R'', wherein R’, R, R' are independantly Selected from hydrogen, alkyl, and aryl, and n is from 1 to 2O. 0.091 In an additional embodiment, the functional group on the functionalized diamondoid may be -N=C=S; N=C=O; R-N=C=O; R-N=C=S; -N=S=O; or -R-N=S=O wherein R is alkyl;-PH; -POX wherein X is halo; -PO(OH); -OSOH: wherein R, R, R, R and R are hydrogen or alkyl; -SOH, -SOX wherein X is halo, -SOR wherein R is R", R, R, and R7 are independently absent or hydrogen alkyl, -SOOR wherein R is alkyl, -SONRR’7 wherein or alkyl with the proviso that at least one of R', R, R, R° and R are independently hydrogen or alkyl, -Ns; and R is present; and n and m are independently from 2 to –OC(O)Cl; or –OC(O)SC1. 20 or the like. The counterion may any acceptable monova 0092. In a further aspect, the functionalizing group may lent anion, for example, halogen, hydroxide, Sulfate, nitrate, form a covalent bond to two or more diamondoids and thus phosphate, and the like. Serves as a linking group between the two or more diamon 0094. In another aspect, the present invention relates to doids. This provides functionalized diamondoids of Formula functionalized diamondoids of Formula III: II: wherein each D is a diamondoid nucleus and Rand Rare Substituents on the diamondoid nucleus and are indepen wherein D is a diamondoid nucleus and L is a linking group dently hydrogen or a functionalizing group. Preferably the and n is 1 or more Such as 1 to 10 and especially 1 to 4. material contains either 1 or 2 functional groups. Preferably 0093. In this embodiment, the linking group L may be RandR'' are halo; cyano; aryl; arylalkoxy; aminoalkyl; or -N=C-N- -COOR' wherein R' is hydrogen or alkyl. 0095. In an additional aspect, the present invention pro vides Salts, individual isomers, and mixtures of isomers of R28 R29 diamondoid derivatives of Formulae I, II, and III. 0096 Turning now to the derivatization reaction of dia mondoids, there are three different carbons in the diamon US 2006/0057496 A1 Mar. 16, 2006 doids skeleton: quaternary (4 or C-4), tertiary (3 or C-3), 0099. Of those SN1 and S2 reactions, SN 1-type reactions and secondary (2 or C-2) carbons. Of those different are the most frequently used for the derivatization of dia carbons, quaternary carbons are impossible to perform any mondoids. However, Such reactions produce the derivatives kind of reactions on. Chemical reactions can only take place mainly substituted at the tertiary carbons. Substitution at the on those tertiary (3 or C-3) and secondary (20 or C-2) Secondary carbons of diamondoids is not easy in carbonium carbons in the diamondoid skeletons. It should be mentioned ion processes Since Secondary carbons are considerably leSS that Some of the tertiary or Secondary carbons are equivalent. reactive than the bridgehead positions (tertiary carbons) in This means that the derivatives Substituted at those equiva ionic processes. However, reactions at the Secondary car lent tertiary or Secondary carbons are identical. bons are achieved by taking advantage of the low Selectivity 0097 FIG. 5 shows a flow chart for the strategy of of free radical reactions and the high ratios of 2 (secondary) derivatization of diamondoids and FIG. 6 shows some to 3 (tertiary, bridgehead) hydrogens in diamondoids. Thus, representative primary derivatives of diamondoids and the free radical reactions provide a method for the preparation of corresponding reactions. AS shown in FIG. 6, there are, in a greater number of the possible isomers of a given diamon general, three major reactions for the derivatization of doid than might be available by ionic precesses. The com diamondoids Sorted by mechanism: nucleophilic (SN 1-type) pleX product mixtures and/or isomers which result, however, and electrophilic (S.2-type) Substitution reactions, and free are generally difficult to Separate. Due to the decreased radical reaction (details for Such reactions and their use with Symmetry of Substituted diamondoids, free radical Substitu adamantane are shown, for instance in, “Recent develop tion of these Substrates may give rise to very complex ments in the adamantane and related polycyclic hydrocar product mixtures. Therefore, in most cases, practical and bons' by R. C. Bingham and P. V. R. Schleryer as a chapter useful free radical Substitutions of diamondoids can use of the book entitled “Chemistry of Adamantanes” (Springer photochlorination and/or photooxidation under Special cir Verlag, Berlin Heidelberg New York, 1971) and in; “Reac cumstances which permit a simpler Separation of the product tions of adamantanes in electrophilic media” by I. K. mixture. For instance, photochlorination is particularly use Moiseev, N. V. Makarova, M. N. Zemtsova published in ful for the synthesis of chlorinated diamondoids at the Russian Chemical Review, 68(12), 1001-1020 (1999); Secondary carbons and further derivatizations at the Second “Cage hydrocarbons' edited by George A. Olah (John Wiley ary carbons because chlorinated diamondoids at the Second & Son, Inc., New York, 1990). ary carbons are similar in reactivity to those derivatized at 0.098 SN1 reactions involve the generation of diamon the tertiary carbons. doid carbocations (there are several different ways to gen 0100 Photooxidation is another powerful free radical erate the diamondoid carbocations, for instance, the carboca reaction for the synthesis of hydroxylated derivatives at the tion is generated from a parent diamondoid, a hydroxylated Secondary carbons which are further oxidized to keto deriva diamondoid or a halogenated diamondoid, shown in FIG. tives, which can be reduced to alcohols providing unique 7), which Subsequently react with various nucleophiles. hydroxylated diamondoid derivatives at the Secondary car Some representative examples are shown in FIG. 8. Such bons. nucleophiles include, for instance, the following: water (providing hydroxylated diamondoids); halide ions (provid 0101 Considering this significant advantage of Separat ing halogenated diamondoids); ammonia (providing ami ing the keto diamondoids, a variety of diamondoid deriva nated diamondoids); azide (providing azidylated diamon tives at the Secondary carbons are prepared Starting from the doids); nitriles (the Ritter reaction, providing aminated keto derivatives (diamondoidones), Such as by reducing the diamondoids after hydrolysis); carbon monoxide (the Koch keto group by, for instance, LiAlH, to provide the corre Haaf reaction, providing carboxylated diamondoids after sponding hydroxylated derivatives at the Secondary carbons hydrolysis), olefins (providing alkenylated diamondoids and further derivatizations at the Secondary carbons Starting after deprotonation); and aromatic reagents (providing ary from those hydroxylated derivatives. Diamondoidones can lated diamondoids after deprotonation). The reaction occurs also undergo acid-catalyzed (HCl-catalyzed) condensation Similarly to those of open chain alkyl Systems, Such as reaction with, for example, excess phenol or aniline in the t-butyl, t-cumyl and cycloalkyl Systems. Since tertiary presence of hydrogen chloride to form 2,2-bis(4-hydrox (bridgehead) carbons of diamondoids are considerably more yphenyl) diamondoids or 2,2-bis(4-aminophenyl) higher reactive than Secondary carbons under SN1 reaction condi diamandoids substituted at the secondary carbons. With the tions, Substitution at the tertiary carbons is favored. S.2-type development of Separation technology, Such as by using reactions (i.e., electrophile substitution of a C-H bond via up-to-date HPLC technique, we may predict that more free a five-coordinate carbocation intermediate) include, for radical reactions might be employed for the Synthesis of instance, the following reactions: hydrogen-deuterium derivatives of diamondoids. exchange upon treatment with deuterated Superacids (e.g., 0102) Using those three major types of reactions for the DF-SbF, or DSO.F-SbF5); nitration upon treatment with derivatization of diamondoids, a number of diamondoid nitronium salts, such as NOBF or NOPF in the derivatives are prepared. Representative core reactions and presence of Superacids (e.g., CFSOH), halogenation upon, the derivatives are presented as following as either very for instance, reaction with Cla--AgSbF, alkylation of the important means to activate the diamondoid nuclei or very bridgehead carbons under the Friedel-Crafts conditions (i.e., S2-type O alkylation); carboxylation under the Koch reac important precursors for further derivatizations. tion conditions; and, oxygenation under S2-type a 0.103 FIG. 10 shows some representative pathways for hydroxylation conditions (e.g., hydrogen peroxide or OZone the preparation of brominated diamondoid derivatives. using Superacid catalysis involving HO or HO, respec Mono- and multi-brominated diamondoids are Some of the tively). Some representative SE-type reactions are shown in most versatile intermediates in the derivative chemistry of FIG 9. diamondoids. These intermediates are used in, for example, US 2006/0057496 A1 Mar. 16, 2006
the Koch-Haaf, the Ritter, and the Friedel-Crafts alkylation/ diamondoid nuclei for further derivatizations, Such as the arylation reactions. Brominated diamondoids are prepared generation of diamondoid carbocations under acidic condi by two different general routes. One involves direct bromi tions, which undergo the SN1 reaction to provide a variety nation of diamondoids with elemental bromine in the pres of diamondoid derivatives. In addition, hydroxylated deriva ence or absence of a Lewis acid (e.g. BBr-AlBra) catalyst. tives are very important nucleophilic agents, by which a The other involves the substitution reaction of hydroxylated variety of diamondoid derivatives are produced. For diamondoids with hydrobromic acid. instance, the hydroxylated derivatives are esterified under Standard conditions Such as reaction with an activated acid 0104 Direct bromination of diamondoids is highly selec derivative. Alkylation to prepare etherS is performed on the tive resulting in Substitution at the bridgehead (tertiary) hydroxylated derivatives through nucleophilic Substitution carbons. By proper choice of catalyst and conditions, one, on appropriate alkyl halides. two, three, four, or more bromines can be introduced Sequen tially into the molecule, all at bridgehead positions. Without 0110. The above described three core derivatives a catalyst, the mono-bromo derivative is the major product (hydroxylated diamondoids and halogenated especially bro with minor amounts of higher bromination products being minated and chlorinated diamondoids), in addition to the formed. By use of Suitable catalysts, however, di-, tri-, and parent diamondoids or Substituted diamondoids directly tetra-, penta-, and higher bromide derivatives of diamon Separated from the feedstocks as described above, are most doids are isolated as major products in the bromination (e.g., frequently used for further derivatizations of diamondoids, adding catalyst mixture of boron bromide and aluminum Such as hydroxylated and halogenated derivatives at the bromide with different molar ratios into the bromine reaction tertiary carbons are very important precursors for the gen mixture). Typically, tetrabromo or higher bromo derivatives eration of higher diamondiod carbocations, which undergo are Synthesized at higher temperatures in a Sealed tube. the SN1 reaction to provide a variety of diamondoid deriva tives thanks to the tertiary nature of the bromide or chloride 0105 To prepare bromo derivatives substituted at Sec or alcohol and the absence of skeletal rearrangements in the ondary carbons, for example, the corresponding hydroxy Subsequent reactions. Examples are given below. lated diamondoids at the Secondary carbons is treated under mild conditions with hydrobromic acid. Preferably, diamon 0111 FIG. 13 shows some representative pathways for doids hydroxylated at Secondary carbons are prepared by the the Synthesis of carboxylated diamondoids, Such as the reduction of the corresponding keto derivative as described Koch-Haaf reaction, Starting from hydroxylated or bromi above. nated diamondoids. It should be mentioned that for most cases, using hydroxylated precursors get better yields than 0106 Bromination reactions of diamondoids are usually using brominated diamondoids. For instance, carboxylated worked up by pouring the reaction mixture onto ice or ice derivatives are obtained from the reaction of hydroxylated water and adding a Suitable amount of chloroform or ethyl derivatives with formic acid after hydrolysis. The carboxy ether or carbon tetrachloride to the ice mixture. ExceSS lated derivatives are further esterified through activation bromine is removed by distillation under vacuum and addi (e.g., conversion to acid chloride) and Subsequent exposure tion of Solid sodium disulfide or sodium hydrogen sulfide. to an appropriate alcohol. Those esters are reduced to The organic layer is separated and the aqueous layer is provide the corresponding hydroxymethyl diamondoids extracted by chloroform or ethyl ether or carbon tetrachlo (diamondoid substituted methyl alcohols, D-CH-OH). ride for an additional 2-3 times. The organic layers are then Amide formation is also performed through activation of the combined and washed with aqueous Sodium hydrogen car carboxylated derivative and reaction with a Suitable amine. bonate and water, and finally dried. Reduction of the diamondoid carboxamide with reducing 0107 To isolate the brominated derivatives, the solvent is agents (e.g. lithium aluminum hydride) provides the corre removed under Vacuum. Typically, the reaction mixture is sponding aminomethyl diamondoids (diamondoid Substi purified by Subjecting it to column chromatography on either tuted methylamines, D-CH-NH). alumina or Silica gel using Standard elution conditions (e.g., 0112 FIG. 14 shows some representative pathways for eluting with light petroleum ether, n-hexane, or cyclohexane the Synthesis of acylaminated diamondoids, Such as the or their mixtures with ethyl ether). Separation by preparative Ritter reaction Starting from hydroxylated or brominated gas chromatography (GC) or high performance liquid chro diamondoids. Similarly to the Koch-Haaf reaction, using matography (HPLC) is used where normal column chroma hydroxylated precursors get better yields than using bromi tography is difficult and/or the reaction is performed on nated diamondoids in most cases. Acylaminated diamon extremely Small quantities of material. doids are converted to amino derivatives after alkaline 0108 Similarly to bromination reactions, diamondoids hydrolysis. Amino diamondoids are further converted to, are chlorinated or photochlorinated to provide a variety of without purification in most cases, amino diamondoid mono-, di-, tri-, or even higher chlorinated derivatives of the hydrochloride by introducing hydrochloride gas into the diamondoids. FIG. 11 shows some representative pathways aminated derivatives Solution. Amino diamondoids are Some for the synthesis of chlorinated diamondoid derivatives, of very important precursors in the Synthesis of medicines. especially those chlorinated derivatives at the Secondary They are also prepared from the reduction of nitrated com carbons by way of photochlorination. pounds. FIG. 15 shows some representative pathways for the synthesis of nitro diamondoid derivatives. Diamondoids 0109 FIG. 12 shows some representative pathways for are nitrated by concentrated nitric acid in the presence of the synthesis of hydroxylated diamondoids. Direct hydroxy glacial acetic acid under high temperature and preSSure. The lation is also effected on diamondoids upon treatment with nitrated diamondoids are reduced to provide the correspond N-hydroxyphthalimide and a binary co-catalyst in acetic ing amino derivatives. In turn, for Some cases, amino acid. Hydroxylation is a very important way of activating the diamondoids are oxidized to the corresponding nitro deriva US 2006/0057496 A1 Mar. 16, 2006 tives if necessary. The amino derivatives are also synthe 0118 Diamondoidones or “diamondoid oxides” are syn sized from the brominated derivatives by heating them in the thesized by photooxidation of diamondoids in the presence presence of formamide and Subsequently hydrolyzing the of peracetic acid followed by treatment with a mixture of resultant amide. chromic acid-Sulfuric acid. Diamondoidones are reduced by, 0113 Similarly to the hydroxylated compounds, amino for instance, LiAlH, to diamondoidols hydroxylated at the higher diamonds are acylated or alkylated. For instance, Secondary carbons. Diamondoidones also undergo acid reaction of an amino diamondoid with an activated acid catalyzed (HC1-catalyzed) condensation reaction with, for derivative produces the corresponding amide. Alkylation is example, excess phenol or aniline in the presence of hydro typically performed by reacting the amine with a Suitable gen chloride to form 2,2-bis(4-hydroxyphenyl) diamondoids carbonyl containing compound in the presence of a reducing or 2,2-bis(4-aminophenyl) diamondoids. agent (e.g. lithium aluminum hydride). The amino diamon 0119) Diamondoidones (e.g. D=O) are treated with doids undergo condensation reactions with carbamates Such RCN(R=hydrogen, alkyl, aryl, etc.) and reduced with as appropriately Substituted ethyl N-arylsulfonylcarbamates LiAlH, to give the corresponding C-2-aminomethyl-C-2-D- in hot toluene to provide, for instance, N-arylsulfonyl-N'- OH, which are heated with COCl or CSC1 in toluene to diamondoidylureas. afford the following derivatives shown in formula IV (where 0114 FIG. 16 presents some representative pathways for Z=O or S): the Synthesis of alkylated, alkenylated, alkynylated and arylated diamondoids, Such as the Friedel-Crafts reaction. IV Ethenylated diamondoid derivatives are synthesized by R reacting a brominated diamondoid with ethylene in the presence of AlBr followed by dehydrogen bromide with potassium hydroxide (or the like). The ethenylated com pound is transformed into the corresponding epoxide under O)- Standard reaction conditions (e.g., 3-chloroperbenzoic acid). Oxidative cleavage (e.g., ozonolysis) of the ethenylated diamondoid affords the related aldehyde. The ethynylated 0120 Diamondoidones react with a suitable primary diamondoid derivatives are obtained by treating a bromi amine in an appropriate Solvent to form the corresponding nated diamondoid with vinyl bromide in the presence of imines. Hydrogenation of the imines in ethanol using Pd/C AlBr. The resultant product is dehydrogen bromide using as the catalyst at about 50 C. to afford the corresponding KOH or potassium t-butoxide to provide the desired com Secondary amines. Methylation of the Secondary amines pound. following general procedures (see, for instance, H. W. Geluk 0115 More reactions are illustrative of methods which and V. G. Keiser, Organic Synthesis, 53:8 (1973)) to give the can be used to functionalize diamondoids. For instance, corresponding tertiary amines. Quaternization of the tertiary fluorination of a diamondoid is carried out by reacting the amines by, for instance, slowly dropping CHI (excess) into diamondoid with a mixture of poly(hydrogen fluoride) and an ethanol solution of the amine at around 35° C. to form the pyridine (30% Py, 70% HF) in the presence of nitronium corresponding quaternary amines. tetrafluoroborate. Sulfur tetrafluoride reacts with a diamon 0121 C-2 derivatives of diamondoids, C-2 D-R' (R'= doid in the presence of sulfur monochloride to afford a alkyl, alkoxy, halo, OH, Ph, COOH, CHCOOH, mixture of mono-, di-, tri- and even higher fluorinated NHCOCH, CFCOOH) are prepared by nucleophilic Sub diamondoids. Iodo diamondoids are obtained by a Substitu stitution of diamondoid-C-2-spiro-C-3-diazirine in solution tive iodination of chloro, bromo or hydroxyl diamondoids. at 0-80 C. in the presence of an acid catalyst. 0116 Reaction of the brominated derivatives with hydro chloric acid in dimethylformamide (DMF) converts the 0122) N-sulfinyl diamondoids D-(NSO), n=1, 2, 3, 4, . compounds to the corresponding hydroxylated derivatives. . . are prepared by refluxing the diamondoid-HCl with Brominated or iodinated diamondoids are converted to thi SOCl, in benzene for about half an hour to several hours olated diamondoids by way of, for instance, reacting with afording mono-, di, tri-, or higher N-Sulfinyl diamondoid thioacetic acid to form diamondoid thioacetates followed by derivatives. removal of the acetate group under basic conditions. Bro 0123 Treatment of D-Brand/or D-Cl with HCONH (wt. minated diamondoids, e.g. D-Br, is heated under reflux with ratio not >1:2) at <195 C. followed by hydrolysis of the an excess (10 fold) of hydroxyalkylamine, e.g. formylamino diamondoids D-NHCHO with <20% HCl at HO-CHCH-NH, in the presence of a base, e.g. tri <110° C. affords the amino diamondoid hydrochloride ethylamine, diamondoidyloxyalkylamine, e.g. D-O- CHCH-NH, is obtained. On acetylation of the amines with acetic anhydride and pyridine, a variety of N-acetyl 0.124 Diamondoid dicarboxamides are prepared by the derivatives are obtained. Direct Substitution reaction of reaction of diamondoid dicarbonyl chloride or diamondoid brominated diamondoids, e.g. D-Br, with Sodium azide in diacetyl chloride with aminoalkylamines. For instance, dipolar aprotic solvents, e.g. DMF, to afford the azido D-(COCl), from SOC1 and the corresponding dicarboxylic diamondoids, e.g. D-N. acid D-(COOH). C treated with (CH).NCHCHCH-NH in C.H.N-C.H., to give N,N'- 0117 Diamondoid carboxylic acid hydrazides are pre bis(dimethylaminopropyl) diamondoid dicarboxamide. pared by conversion of diamondoid carboxylic acid into a chloroanhydride by thionyl chloride and condensation with 0.125 Aminoethoxyacetylamino diamondoids are pre isonicotinic or nicotinic acid hydrazide (FIG. 17). pared from chloroacetylamino diamondoids and US 2006/0057496 A1 Mar. 16, 2006
HOCH2CHNR'R". Thus, for instance, amino diamondoids, mondoid nucleus to form an ester, and the unsaturated acid D-NH, and CICH2COCl in benzene, is added to residue may comprise an acrylate or a lower alkyl acrylate. (CH)NCHCHONa in Xylene and refluxed for about 10 When the unsaturated acid residue is an acrylic acid residue hours to give aminoethoxyacetylamino diamondoids the respective monomer becomes an acrylate monomer. Similarly, when the unsaturated acid residue is an meth 0126 Ritter reaction of C-3 D-OH and HCN gives acrylic acid residue the respective monomer becomes an D-NH; the preparation of D-NHCHO from diamondoids methacrylate monomer. and HCN; the reaction of diamondoids with nitriles gives 0134) Further embodiments of the present invention pro D-NHCHO and D-NH; the preparation of aza diamondoids vide for methods of forming a layer of patterned photoresist from nitriles and compounds containing unsaturated OH on the Surface of a Substrate. Such methods comprise the groups, and SH groups, and So on. Steps of 0127 Hydroxylated diamondoids, e.g. D-OH, react with 0135) a) forming a polymer from monomers selected COCl or CSC1 to afford the diamondoidyloxycarbonyl from the group consisting of a diamantyl monomer derivatives, e.g. D-O-C(O)C1 or D-O-C(S)C1 the former having a polymerizable group and at least one hydro being an important blocking group in biochemical Synthe philic-enhancing group; a triamantyl monomer having SCS. a polymerizable group and at least one hydrophilic enhancing group; and a diamondoid-containing mono 0128 FIG. 18 shows representative reactions starting mer having a polymerizable group and at least one from D-NH and D-CONH2 and the corresponding deriva hydrophilic-enhancing group, the diamondoid of the tives, wherein D is a diamondoid nucleus. diamondoid-containing monomer Selected from the 0129 FIG. 19 shows representative reactions starting group consisting of tetramantane, pentamantane, hexa from D-POCl and the corresponding derivatives, wherein D mantane, heptamantane, octamantane, nonamantane, is a diamondoid nucleus. decamantane, and undecamantane, 0130 FIG. 20 shows representative reactions starting 0136 b) depositing the polymer on a surface of the from D-SH or D-SOCl and the corresponding derivatives, Substrate as a polymeric layer, the polymeric layer wherein D is a diamondoid nucleus. comprising a photo-labile polymer; and Polymerizable Diamantyl, and Triamanty1 and Higher Dia 0137 c) exposing selected regions of the polymerized mondoid Containing Monomers layer to an electromagnetic beam, thereby modifying 0131 Embodiments of the present invention specifically the photo-labile polymer in those regions exposed to include polymerizable diamantyl monomers having the for the electromagnetic beam to yield a Selectively modi mula Pg-D-(R), wherein D is a diamantyl nucleus, Pg is a fied layer. polymerizable group covalently bonded to a carbon of the diamantyl nucleus; n is an integer ranging from 1 to 6, 0.138 According to further embodiments, the method inclusive; at least one of the RS is a hydrophilic-enhancing described above may include the Step of contacting the moiety; and each of the remaining R's is independently selectively modified layer with a solvent system to solubilize Selected from the group consisting of hydrogen and a the modified regions. The electromagnetic beam may com hydrophilic-enhancing moiety. The hydrophilic-enhancing prise radiation having a wavelength less than about 200 nm, moietyies of these diamantyl monomerS may be Selected and exemplary wavelenths are 193 nm and 157 nm. The from the group consisting of a hydroxyl group -OH, a electromagnetic beam may also be an e-beam or an X-ray carboxylic group -COOH, an alkyl group -OCH or beam. -OCH5, a keto group -C(O)-, and a group 0.139. As will be explained, one excellent application for —OC(O)OCH, or —OC(O)OC.H. these monomers and polymerS is as components of photo 0132). Other embodiments of the present invention pro resists. In this application the monomers and polymers can vide for triamantyl monomers having polymerizable groups Serve as components of deposited layers. These layers are and hydrophilic-enhancing moities similar to those for dia additional aspects of this invention as are patterned layers mantyl monomers discussed above, as well as diamonoid and methods of preparing them all of which employ the containing monomers with polymerizable groups and hydro instant diamantyl and/or triamantyl monomers and poly philic-enhancing moities, wherein the diamondoid portion CS. of the diamonoid-containing monomer is Selected from the Photoresist Base Resins group consisting of tetramantane, pentamantane, heXaman 0140 Prior art polymers that have been used in positive tane, heptamantane, octamantane, nonamantane, decaman acting photoresists have been discussed by K. Nozaki and E. tane, and undecamantane. Yano in “High-Performance Resist Materials for Arf 0133. In other embodiments of the present invention, the Eximer Laser and Electron Beam Lithography,” Fujitsu Sci. the polymerizable groups Pg of the diamantyl, triamantyl, Tech.J., 38, 1, p. 3-12 (June, 2002). These authors teach that higher diamondoid containing monomers are capable of conventionally, polyvinylphenol-based resists were gener forming photo-labile polymers. The polymerizable groups ally used in electron bearm lithography, and Such resins may be covalently bonded to either Secondary (2) carbons or made use of a variety of protecting groupS. Such as acetals, tertiary carbons (3, also called bridgehead carbons) of the tert-butoxycarbonyl, and tert-butyl. The disadvantages of diamantyl, triamantyl, or higher diamondoid nucleus. These these protecting groups included a poor dry-etch resistance polymerizable groups may comprise an unsaturated acid due to the aliphatic Structures. To overcome this problem, K. residue bound to the diamantyl, triamantyl, or higher dia Nozaki and E. Yano Suggested the use of acid Sensitive and US 2006/0057496 A1 Mar. 16, 2006 dry etch resistant protective groups. These authors teach that represented by the general formula illustrated in FIGS. dry etch resistance may be imparted to the resist by incor 21A-C. The positive-working photoresist composition porating acid cleavable alicyclic Substituents into the base shown in FIG. 21A comprises a polymeric backbone chain polymer. 210, which may include pendant groups 212. The pendant 0141 K. Nozaki and E. Yano reported on the use of groupS 212 may be a non-diamondoid pendant group rep mevalonic lactone methacrylate (MLMA) and 2-methyl-2- resented by P, or the pendant groups may be diamondoid adamantane methacrylate (MAdMA) based copolymers. containing Such as the adamantane based pendant group 214 The adamantyl, polycyclic hydrocarbon Substituent pro or the diamantane based pendant group 216. In this example, Vided Superior Sensitivity, resolution, and dry etch resis the pendant groupS 212 are connected to the main backbone tance, whereas the lactone containing monomer afforded chain 210 through ester groups 218, which is the linkage that compatibility with conventional developerS Such as tetram imparts the acid-cleavable character to the base resin shown ethylammonium hydroxide (TMAH), and adhesion to sili in FIG. 21A. Also depicted in FIG. 21 A are alkyl groups con Substrates. The adamantane and lactone Substituents R. that yield a tertiary alcohol when the blocking groups 214 were chosen Since they can function as acid labile ester and 216 are cleaved, as well as hydrophilic-enhancing groups in the methacrylate polymer. The hydrophilic meva groupS Rs. lonic lactone group provided adhesion to the Silicon Sub 0145 Specifically, in this exemplary base resin, R may Strate, and was acid cleavable because it contained an acid be either -H or -CH, such that the polymeric backbone Sensitive B-hydroxyketone structure and a tertiary alcohol. chain 210 constitutes either an acrylate type polymer, or a The alicyclic adamantyl Substituent provided dry etch resis methacrylate type polymer, respectively. R2 in this example tance, and was also acid cleavable because of a tertiary may be either -H, in which case the diamondoid-contain alcohol. These authors teach that the adamantyl groups have ing monomer is not acid cleavable, or an alkyl (Such as a stronger dissolution inhibition than, for example, a t-butyl -CH) group having from 1 to 4 carbon atoms. In the latter pendant group would have, which comes about from its case the diamondoid-containing pendant group is acid cleav highly hydrophobic nature and bulky Structure. Thus, a large able because the capablility of forming a carbon-carbon polarity change can be obtained with a Small amount of double bond exists. The dissolution ability of the pendant deprotection, and therefore a Superior contrast between group (i.e., the ability of the pendant group to dissolve in an exposed and unexposed regions of the resist may be realized, alkali developer) is enhanced by the fact that a tertiary contributing to enhance resolution. alcohol is formed when R is an alkyl group or an alkoxy 0142. Of particular interest is the imaging results group. R is either -H, or a hydrophilic-enhancing moiety obtained by K. Nozaki and E. Yano. A series of five that may be either a hydroxyl group -OH, a carboxylic methacrylate polymers were prepared, wherein the ratioS of gropup -COOH, an alkyl group -OR, a keto group the monomers MLMA/MAdMA ranged from 0/100, 22/78, -C(O)-, or -OC(O)-OR. It will be apparent to those 51/49, 72/28, and 100/0, respectively. The polymers pre skilled in the art that -OR represents the Situation when an pared from the latter two monomer ratioS could not be alcohol group -OH is protected, wherein the protection imaged because they were alkali Soluble, and it was not may be in the form of an alkyl group or an acetate group. possible to resolve any resist patterns. Furthermore, the 0146) One feature of the present embodiments that con polymer prepared from the 100/0 ratio was difficult to tribute to their novelty is the fact that, unlike the base spin-coat because the photo-acid generator Separated out polymers taught by K. Nozaki and E. Yano, a monomer from the resist composition. The polymers prepared from the having a diamondoid pendant group higher than adamantane first two monomer ratios likewise did not image well (or is included in the base resin. This exemplary monomer that could not be imaged) because the formulated resist patterns contains a pendant group higher than adamantane is shown peeled off the Silicon Substrates, Suggesting that the rigid in FIG. 21A as diamantane. The advantages of including adamantyl units imparted a brittleness to the resist. The monomers with diamondoid-containing pendant groups photoresist composition containing roughly equal amounts higher than adamantane is that Since because there are more of the two monomers was thought to be a promising com carbons present in the Sp-hybridized, diamond cubic crystal promise, and based on their observations, the optimum Structure, the blocking group is more resistant to the etching composition for the base polymer was about MAdMA/ process, and thus, the exposed and unexposed regions of the MLMA=1/1. resist are more delineated. This feature enhances resolution. 0143. The photoresist compositions of the present Furthermore, because the etch resistance has been improved, embodiments include acid-cleavable diamondoid blocking it may be possible to incorporate less of the diamantane groups higher in the homologous Series than adamantane. containing monomer into the base resin, improving the The advantages of including Such diamondoids is that an ability of the resist to adhere to the substrate. enhanced etch resistance may be imparted to the base resin, 0147 According to embodiments of the present inven thereby improving the resolution of the resist, but the choice tion, the ratios of the feed monomers for the exemplary base of diamondoid higher than adamantane, the amounts in resin depicted in FIG. 21A may be represented by the which it is used, and the number of hydrophilic-enhancing relationships: groups with which it is derivatized, comprise a part of the Subject matter of the present disclosure. 0148 a is 0.25 to 0.75; Co-Polymer Base Resins with Diamondoids Hither than 014.9 b+c=1-a; and Adamantane O150 c is greater than Zero, 0144. According to embodiments of the present inven where a, b, and c represent the relative amounts of the tion, the base resin of a positive-acting photoresist may be non-diamondoid containing monomer, the adamantane US 2006/0057496 A1 Mar. 16, 2006 13
containing monomer, and the diamantane-containing FIG. 22A. The tetramantane pendant group 224 is attached monomer, respectively. It will be understood by those to the main polymer chain by ester linkage 226, as before. skilled in the art that the formula shown in FIG. 21A The tetramantane molecule is shown as containing Substitu is Schematic only, and that the repeat units represented ents R., R., R., and Rs, and the nomenclature in FIG. 22A in quantities a, b, and c may appear in Virtually any is meant to indicate that these Substituents may be attached order in the polymer chain. In other words, the repeat at a number of possible sites to the tetramantane carbon units do not have to follow the pattern a, b, c, a, b, c, framework (secondary and tertiary carbons shown in FIGS. and may instead take the form a, a, b, a, c, a, b, b, a, b, 22B-E). It will become apparent to the reader that one of the c., a, c, b, etc. advantages of including diamondoid-containing pendant groups higher than adamantane are the vast number of 0151. A consequence of including monomers with dia possible attachment sites for hydrophilic-enhancing groups, mondoid-containing pendant groups higher than adaman alkyl groups, and polymerizable groups. tane is that the pendant group will be more hydrophobic, and thus it will be more difficult to dissolve the blocking group Etch Resistance in the alkali developer. This issue may be addressed, how 0156 The inclusion of diamondoid-containing mono ever, by derivatizing the diamantane or higher pendant merS higher than adamantane is contemplated to have the group with a larger number of hydrophilic-enhancing advantageous result of imparting enhanced etch resistance to groups, Such as the -OH group Rs. The number of these the polymer. AS discussed in a reference titled “Lithographic that are required is also the Subject matter of the present Resists,” by W. D. Hinsberg et al. (IBM Research Division, disclosure. K-Othmer, Encyclopedia of Chemical Technology), a para 0152 The diamondoid-containing monomer having a mater was devised by Ohnishi et al. to correlate a photore pendant group higher than adamantane is not limited to Sist's chemical composition with its ability to withstand an diamantane, and may in fact comprise triamantane 220, and etching environment. The parameter is given by N/(N-N), diamondoids 222 that are even higher than triamantane in where N is the total number of atoms in the polymer repeat the polymantane hydrocarbon Series. This is illustrated in unit, including hydrogen atoms, N is the number of carbon FIG 21B. The term “diamondoid in FIG 21B is meant to atoms, and N is the number of oxygen atoms. represent any of the diamondoids tetramantane, pentaman O157 The model serves as a fair predictor of etch rates tane, heXamantane, heptamantane, octamantane, nonaman for polymers under conditions where physical ion bombard tane, decamantane, and undecamantane. Again, the order of ment is a Significant component, as is the case for reactive the repeat units in the chain is not limited to that shown in ion etching. The relation fails for low ion energy plasma FIG. 21B, as this is just a schematic drawing of an exem conditions, Such as those that what occurred in a down plary polymer. If the polymer contains either or both dia Stream glow discharge process, where etching mechanisms mantane and triamantane, and even diamondoids, the are primarily chemical in nature. The Ohnishi parameter amounts of these repeat units (which may be the same thing predicts that polymers having a high content of carbon (e.g., as Saying the relative amounts of the monomers in the feed, a low Ohnishi number) will exhibit low etch rates. In depending on the reactivity of the monomers during the contrast, incorporation of hydrogen and/or oxygen into the polymerization process), may be represented by c, d, and e, repeat unit Structure increases the etch rate, while an respectively. increased carbon content reduces the etch rate. 0153. In the exemplary polymer of FIG. 21A, P, is a 0158. The Ohnishi numbers for exemplary monomers of non-diamondoid, acid-cleavable pendant group that may be the present invention, with adamantane for comparison, are represented by the structures shown in FIGS. 21C-D. The shown with their respective schematic drawings in FIG. value of “n” may be either 0 or 1. If n=0, then the 23A. Referring to FIG. 23A, an adamantane-containing non-diamondoid pendant group shown in FIG. 21C com prises a five-membered heterocyclic ring with no R. or R, repeat unit has an Ohnishi number of 3.00, while this Substituents on the ring. If n=1, then the non-diamondoid number decreases for diamantane, triamantane, and tetra pendant group shown in FIG. 21 C comprises a five mane as follows: 2.75, 2.60, and 2.50. As taught by the membered heterocyclic ring with Substituents R or R7 on present disclosure, however, it is necessary to include hydro the alpha carbon relative to where the ring attaches to the philic-enhancing groups as Substituents on the diamondoid main polymeric backbone. Again, the linkage in this exem pendant groups, and the number of these hydrophilic-en plary polymer is an ester linkage, making the polymer an hancing groups that are required will increase as the size of acrylate or methacrylate, but many other types of linkages the diamondoid increases. are possible. 0159. It is a surprising result just how many of these hydrophilic-enhancing groups may be tolerated with respect 0154) A six-membered heterocyclic ring for the non to etch resistance. For example, FIG. 23B calculates the diamondoid, acid-cleavable pendant group P is shown in Ohnishi number for the same Series adamantane, diaman FIG.21D. In this case, again exemplary, the substituents R. tane, triamantane, and tetramantane, only an additional or R-7 are always present on the alpha carbon. hydroxyl group is added as a Substituent each time the size 0155. It will be understood by those skilled in the art that of the diamondoid is increased. Even with this additional the nomenclature used in FIGS. 21 A-B is meant to represent "burden' on the etch resistance of the resist, the Ohnishi that there are multiple attachment sites for the exemplary number Still decreases for the Series adamantane with one Substituent groupSR and R onto the carbon framework of hydroxyl substitutent, diamantane with two hydroxyl Sub the pendant diamondoid group. An example of this concept Stituents, triamantane with three hydroxyl Substituents, and is illustrated schematically in FIGS. 22A-E. An exemplary tetramantane with four hydroxyl substituents (3.36, 3.29, diamondoid pendant group tetramantane is shown at 224 in 3.24, and 3.20, respectively). US 2006/0057496 A1 Mar. 16, 2006
Multiple Acid-Labile Sites 0.165. The photoresist compositions of the present embodiments may be developed in an aqueous alkaline 01.60 Embodiments of the present invention include the Solution Such as Sodium hydroxide, potassium hydroxide, ability of the diamondoid containing pendant group to be Sodium carbonate, Sodium Silicate, Sodium metasilicate, cleaved at multiple Sites in the link connecting the pendant aqueous ammonia, a primary amind, ethylamine, n-propy group to the main polymer chain. This is illustrated Sche lamine, a Secondary amine, diethylamine, di-n-butylamine, a matically in FIGS. 24A-D. Referring to FIG. 24A, a poly tertiary amine, triethylamine, methyldiethylamine, an alco merizable group 230, which along with methyl group 232 hol amine, dimethylethanolamine, triethanolamine, a qua and ester group 234 defines this exemplary polymer as a ternary ammonium Salt, tetramethylammonium hydroxide, methacrylate, is attached through a Second ester leakage 236 tetraethylammonium hydroxide, a cyclic amine, pyrrole, and to diamondoid 238. The diamondoid 238 has an alkyl piperidine. Substituent 240 attached to the same carbon atom as the ester linkage 236. For exemplary purposes, a hydroxyl Substituent 0166 The photoresist compositions of the present inven 242 is shown attached to diamondoid 238, which in this case tion further include a photoacid generator Selected from the is a diamantane molecule. group consisting of an onium Salt, a diazonium Salt, an ammonium Salt, a phosphonium Salt, an iodonium Salt, a 0.161 The purpose of multiple ester linkages 234 and 236 Sulfonium Salt, a Selenonium Salt, an arSonium Salt, an is to provide a multiplicity of locations for the acid generated organic halogeno compound, and an organo-metal/organic from the exposure event to cleave pendant diamondoid 238 halide compound. The photoacid generator may have an from the main polymer chain (not shown). The advantages o-nitorbenzyl type protecting group, and it may generate a of providing multiple acid cleaving sites is at least twofold: Sulfonic acid upon photolysis. Furthermore, the photoresist 1) a weaker acid may be used to cleave the diamondoid composition may contain the photo-acid generator in an pendant groups, allowing at the same time for a decreased amount ranging from about 0.01 to 30 weight percent. post exposure bake temperature relative to what otherwise 0.167 The photoresist composition of the present might have been necessary, and 2) a potentially larger embodiments may further include an additive selected from variety of photo-acid generators become available. The the group consisting of a Surface active agent, an organic ability to lower the post exposure bake temperature, to 110 basic compound, an acid decomposable dissolution inhibit C. or less, for example, is highly desirable in the industry ing compound, a dye, a plasticizer, a photoSensitizer, and a because of uniformity considerations. Multiple acid-cleav compound promoting Solubility in a developing Solution, as ing sites are contemplated to be effective for the purposes well as diamondoid derivatives as an additive. cited above because the acid-cleaving proceSS is a diffusion driven one, and having more Sites available means that the EXAMPLES acid molecule does not have to diffuse as far. 0.168. The present invention will be described in detail below in terms of example; however, the present invention 0162 Three more examples of diamondoid-containing is not limited in any way to these examples. The reaction monomers with multiple acid-labile sites are shown in mixture and the products were analyzed and characterized FIGS. 24B, C, and D, wherein the diamondoid in FIG. 24B by gas chromatography/mass spectrometry (GC/MS) to con is a triamantane with a hydroxyl and methyl Substituents, firm the presence of target compounds formed and the purity and the linking group 244 contains three ester linkages; the of the products separated. The GC/MS systems used is an tetramantane in FIG. 24C has acetate and a carboxylic acid HP 5890 Series II Chromatography connected to an HP5973 Substituent groups (and two ester linkages), and the triaman Series MSD (mass selective detector). tane in FIG.24D has two hydroxyl substituents (and three ester linkages). Example 1 0169 47.1 g of diamantane was dissolved in 375 ml of Lactone-Containing Diamondoid Pendant Groups acetic acid, then 4.1 g of N-hydroxyphthalimide (NHPI), 0163 The adhesion enhancing lactone group need not be 0.322 g of Co(acac) (cobalt (II) acetylacetonate) were restricted to the non-diamondoid containing pendant group added into the mixture. The mixture was stirred for about 23 P1 of FIGS. 21A-B. An exemplary polymer containing hours at around 75 C. in a bubbling oxygen atmosphere. lactone groups in both the non-diamondoid and the diamon During the reaction, an additional portion of NHPI and doid-containing pendant groups is shown in FIGS. 25A-B. Co(acac), were added. After cooling down to room tempera ture (20° C.) and filtrating off the precipitated unreacted Fully Formulated Resists diamantane, the orange colored reaction mixture was con centrated under Vacuum to give a dark red oily liquid. The 0164. The photoresist composition may further include a dark red oily liquid was dissolved in methylene chloride. Solvent Such as ethylene dichloride, cyclohexanone, cyclo The methylene chloride solution of the reaction mixture was pentanone, 2-heptanone, Y-butyrolactone, methyl ethyl first extracted with water for several times. The combined ketone, ethylene glycol monomethyl ether, ethylene glycol water layers were then extracted with methylene chloride for monoethyl ether, 2-methoxyethyl acetate, ethylene glycol a few times and finally the combined organic layers were monoethyl ether acetate, propylene glycol monomethyl concentrated and Subjected to Silica gel column chromatog ether (PGME), propylene glycol monomethyl ether acetate raphy, thus producing di-hydroxylated diamantane with (PGMEA), ethylene carbonate, toluene, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropi yields of about 30%. The conversion rate of the diamantane onate, ethyl ethoxypropionate, methyl methoxypropionate, was about 64%. ethyl pyruvate, propyl pyruvate, N,N-dimethylformamide, Example 2 dimethylsulfoxide, N-methylpyrrolidone, and tetrahydrofu 0170 A mixture of 9.42 g of diamantane, 0.82 g of a. N-hydroxyphthalimide (NHPI), 0.064 g of Co(acac) (cobalt US 2006/0057496 A1 Mar. 16, 2006
(II) acetylacetonate) and 75 ml of acetic acid was stirred for precipitate a Solid. After filtration and decoloring by acti about 23 hours at around 75 C. in an oxygen bubbling vated carbon as above, the solids were analysized by GC/MS atmosphere. During the reaction, an additional portion of to show the presence of tetra-hydroxylated diamantane. NHPI and Co(acac) were added. After cooling down to room temperature (20 C.), the reaction mixture was then Example 8 concentrated and Subjected to Silica gel column chromatog 0176 Methacryloyl chloride was added dropwise to a raphy, thus producing di- and tri-hydroxylated diamantane Stirred Solution of an equimolar amount of di-hydroxylaed with yields of about 30% and 20% respectively. diamantine, exceSS triethylamine, and methylene chloride in Example 3 a dry nitrogen atmosphere at around -30 to 0°C. Then the resulting mixture was further stirred for several hours while 0171 A mixture of 18.84 g of diamantane, 1.64 g of maintaining the temperature. The resultant mixture was N-hydroxyphthalimide (NHPI), 0.129 g of Co(acac) (cobalt filtrated, and the filtrate was concentrated under vacuum. (11) acetylacetonate) and 75 ml of acetic acid was stirred for The concentrated mixture was washed with water and brine. about 23 hours at around 75 C. in a bubbling oxygen The water layers were combined and extracted with meth atmosphere. During the reaction; an additional portion of ylene chloride. The organic layers were combined and dried NHPI and Co(acac) were added. The reaction mixture was over anhydrous Na2SO and concentrated in vacuum. concentrated and the concentrated reaction mixture was Finally, the concentrate was Subjected to Silica gel column dissolved in methylene chloride. The methylene chloride chromatography, thus producing mono-hydroxyl diaman Solution of the reaction mixture was first extracted with tane methacrylate (yield: 5%). The conversion rate of the water for several times. The combined water layers were di-hydroxylated diamantane was about 10%. then extracted with methylene chloride for a few times and finally the water was evaporated and the residual was Example 9 Subjected to flash Silica gel column chromatography, thus producing tri-hydroxylated diamantine with yields of about 0177 0.4 g of mono-hydroxylated diamantine was dis 20%. solved in 50 mL of methylene chloride. Methacryloyl chlo ride (0.2 mL) and triethylamine (0.5 mL) were added to the Example 4 Solution at room temperature (20 C.) under dry nitrogen 0172 12.4 g of the crude red oily liquid from water atmosphere. The mixture was stirred at room temperature extractions in Example 1 mainly containing tri-hydroxylated (20° C) under dry nitrogen atmosphere for about 2 hours. diamantine was dissolved in about 200 mL ethyl alcohol. 27 Then the mixture was cooled down to 0° C. and another g of activated carbon (60-100 mesh) was added into the ethyl amount of methacryloyl chloride (0.15 mL) and 50 mg alcohol Solution. The mixture was then stirred for about 3.5 4-DMAP (4-dimethylaminopyridine) in 5 mL cold methyl hours at room temperature (20 C). After filtration, the ene chloride were added into the mixture. The mixture was colorless Solution was concentrated to give a colorleSS oily stirred at 0°C. for 30 minutes and then the cooling bath was liquid. removed. The mixture was again Stirred at room temperature (20°C.) for 3 days. GC-MS of the reaction mixture showed Example 5 the formation of diamantane methacrylate. 0173 600 mL of combined methylene chloride extrac Example 10 tions in Example 1 were added 6 g of activated carbon. The mixture was Stirred for about 20 hours at room temperature 0178) To a 50 mL of methylene chloride were added the (20° C.). After filtration, a pale yellow solution was obtained di-hydroxylated diamantane (5.73 mmol) and methacrylic and the Solvent evaporated to give a pale yellow Solids. The acid (1.1 molar equ.). The mixture was stirred for 15 minutes crude Solids were Subjected to Silica gel column chroma at 0° C. under dry nitrogen. Dicyclohexyl carbodiimide tography, thus producing a colorless Solid of di-hydroxy (DCC, 2.1 molar equ.) and 4-DMAP (0.3 molar equ.) in lated diamantine. about 25 mL cold methylene chloride were added, and the mixture was then stirred for 30 minutes at 0°C. under dry Example 6 nitrogen. The cooling bath was then removed and the 0.174 5g of colorful oily liquid from the water extrac solution allowed to warm to room temperature (about 20 C). tions in Example 3 was dissolved in 70 mL of ethyl alcohol. After being Stirred for 50 hours under nitrogen, the reaction Then 10 g of activated carbon was added and the mixture mixture was filtered through a fine glass frit to yield a clear was stirred for about 3.5 hours at room temperature (20° C.). filtrate and the insoluble urea byproduct as a fine white-grey After filtration, the colorleSS Solution was concentrated to an solid. The clear filtrate was washed with water (3x50 mL), almost colorless oily liquid. The liquid was then dissolved in 5% acetic acid aqueous solution (3x20 mL), and finally 2:1 v/v methylene chloride and THF (tetrahydrofuran). The again with water (3x30 mL). The organic layer was sepa Solution was passed on a flash short Silica gel column eluting rated, dried over anhydrous NaSO, filtered, and the solvent first with 2:1 v/v methylene chloride and THF followed by evaporated. The residual was Subjected to column chroma THF and ethyl alcohol (5:1 v/v). The second fraction was tography to give mono-hydroxyl diamantane methacrylate concentrated to give a colorleSS oily liquid of tri-hydroxy (yield: 50%). The conversion rate of the di-hydroxylated lated diamantane. The first fraction was concentrated to diamantane was about 60%. mainly give a white Solid of di-hydroxylated diamantane. Example 11 Example 7 0179 5.8 mmol of di-hydroxylated diamantane, 6.4 0.175. A portion of the dark red oily liquid in Example 1 mmol of triethylamine and 75 mL of methylene chloride was added a large exceSS amount of methylene chloride to were placed in a three necked round-bottom flask. A mixed US 2006/0057496 A1 Mar. 16, 2006
solution of 5.5 mmol of methacryloyl chloride and 5 mL 86. The method of claim 84, further comprising the step methylene chloride was added dropwise over a period of 5 of dissolving the concentrated product in a Solvent, and then minutes under Stirring with the reaction temperature main extracting the resulting Solution with water to form a water tained at 0°C., and the mixture was future stirred for 3 hours layer and a Solvent layer. at 0°C. under nitrogen. The cooling bath was then removed 87. The method of claim 86, further comprising the step and the mixture was stirred at room temperature (20°C.) for of Subjecting the Solvent layer to Silica gel column chroma 23 hours. At last the temperature was increased to about 30 tography to recover di-hydroxylated diamantanes. C. and the mixture was stirred at the increased temperature 88. The method of claim 86, wherein the Solvent is for 2 more hours while adding 0.25 mL of the acid chloride methylene chloride. and 0.5 mL of triethylamine. An extraction was performed 89. The method of claim 86, further comprising the steps by adding water to the reaction mixture, and the organic of dissolving the water layer in ethyl alcohol to form an ethyl layer was separated, washed with water and brine. The water alcohol Solution, adding activated carbon to the ethyl alco layer was extracted with methylene chloride. The organic hol Solution, and then recovering tri-hydroxylated diaman layers were combined, dried with anhydrous NaSO and tanes from the activated carbon and ethyl alcohol Solution. concentrated in Vacuum. The concentrate was Subjected to 90. The method of claim 86, further comprising the steps Silica gel column chromatography, thus producing mono of: hydroxyl diamantane methacrylate (yield: 40%). The con version rate of the di-hydroxylated diamantane was about a) dissolving the water layer in ethyl alcohol to form an 60%. ethyl alcohol Solution; 0180. Many modifications of the exemplary embodi b) adding activated carbon to the ethyl alcohol solution of ments of the invention disclosed above will readily occur to Step a); those skilled in the art. Accordingly, the invention is to be c) concentrating the activated carbon and ethyl alcohol construed as including all Structure and methods that fall Solution of step b) to a concentrated product; within the Scope of the appended claims. d) dissolving the concentrated product of Step c) in 1-83. (canceled) methylene chloride and tetrahydrofuran, and 84. A method of preparing hydroxylated diamantanes e) passing the dissolved concentrated product of Step d) Selected from the group consisting of di-hydroxylated dia through a Silica gel column to elute a methylene mantane, tri-hydroxylated diamantane, tetra-hydroxylated chloride and tetrahydrofuran fraction and a tetrahydro diamantanes, and mixtures thereof, the method comprising furan and ethyl alcohol fraction. the Steps of: 91. The method of claim 90, further comprising the step a) reacting diamantane with N-hydroxyphthalimide of recovering di-hydroxylated diamantanes from the meth (NHPI) and Co(acac) (cobalt(II) acetylacetonate) in a ylene chloride and tetrahydrofuran fraction. reaction mixture, 92. The method of claim 90, further comprising the step of recovering tri-hydroxylated diamantanes from the tet b) concentrating the reaction mixture to form a concen rahydrofuran and ethyl alcohol fraction. trated product; and 93. The method of claim 84, further comprising the steps c) recovering hydroxylated diamantanes from the concen of dissolving the concentrated product in a large excess of trated product. methylene chloride to precipitate a Solid, and then recover 85. The method of claim 84, further comprising the step ing tetra-hydroxylated diamantane the precipitated Solid. of adding additional portions of N-hydroxyphthalimide 94-96. (canceled) (NHPI) and Co(acac) (cobalt (II) acetylacetonate) to the reaction mixture during step a).