US 20150279654A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0279654 A1 KATO et al. (43) Pub. Date: Oct. 1, 2015

(54) TREATING SOLUTION FOR ELECTRONIC The invention is embodied by a treating solution for elec PARTS, AND PROCESS FOR PRODUCING tronic parts that is an aqueous Solution containing one or two ELECTRONIC PARTS or more of anionic Surface active agents represented by the following formulae (1), (2) and (3), and a process for produc (71) Applicant: FINE POLYMERS CORPORATION, ing an electronic part. Tokyo (JP)

(72) Inventors: Toshitada KATO, Noda-city (JP); (1) Naoya SATO, Noda-city (JP); Shigeru KAMON, Noda-city (JP): Koichiro a-y OGATA, Noda-city (JP) (73) Assignee: FINE POLYMERS CORPORATION, OC Tokyo (JP) (21) Appl. No.: 14/670,785 wherein R. R. and R stands for hydrogen or an alkyl or alkylene group having 1 to 4 carbon atoms, and X (22) Filed: Mar. 27, 2015 stands for a functional group capable of becoming an anionic ion. (30) Foreign Application Priority Data

Mar. 29, 2014 (JP) ...... 2014-07O641 (2) Publication Classification R4 ;: (51) Int. Cl. * N HOIL 21/02 (2006.01) 4NeX CILD II/00 (2006.01) X2 pi CID I/02 (2006.01) CID 3/04 (2006.01) HOIL 2/3 II (2006.01) wherein R stands for hydrogen or an alkyl or alkylene C09K 3/08 (2006.01) group having 1 to 4 carbon atoms, X stands for a func (52) U.S. Cl. tional group capable of becoming an anionic ion, and in CPC ...... H0IL 21/0206 (2013.01): HOIL 21/31 III stands for a natural number of greater than 2. (2013.01); C09K 13/08 (2013.01): CIIDI/02 (2013.01): CI ID3/042 (2013.01): CIID II/0047 (2013.01) (3) (57) ABSTRACT The invention provides an aqueous solution capable of selec tively protecting a nitrogen-containing silicon compound COA4 ex from corrosion by a treating Solution for etching, cleaning or X4 X the like, etching oxygen-containing, carbon-containing sili con in particular, and making a large etch rate difference wherein Rs stands for hydrogen or an alkyl or alkylene between a nitrogen-containing silicon compound and an oxy group having 1 to 4 carbon atoms, and X, and X stands gen-containing silicon compound, and a process for produc for a functional group capable of becoming an anionic ing electronic parts as well. ion. US 2015/0279.654 A1 Oct. 1, 2015

TREATING SOLUTION FOR ELECTRONIC trench formed in it. With this resist pattern as a mask, the PARTS, AND PROCESS FOR PRODUCING insulating film and protective film are etched to form an ELECTRONIC PARTS opening through which the upper Surface of the silicon Sub strate is exposed. Note here that the resist pattern will be FIELD OF THE INVENTION removed by asking or the like after the formation of the opening. Then, the protecting film is used as a mask for 0001. The present invention relates to a treating solution etching of the silicon substrate thereby forming a device for electronic parts that makes it possible to remove silicon isolation trench. oxide or the like in a process of producing electronic parts 0006 Further, the silicon nitride film structure is also Such as semiconductors and display devices, and selectively adopted for a pixel-driving thin-film transistor (TFT) or the protect nitrogen-containing silicon compounds in an etching like in a display device Such as a liquid crystal device. For step, and a process for producing an electronic part using this instance, the ohmic contact layer of a channel portion of the treating Solution as well. thin-film transistor is dry etched, after which a passivation layer in a silicon nitride film form is locally provided. BACKGROUND ART 0007 Thus, the silicon nitride film is increasingly used for 0002. In order to form Large scale integration circuit various electronic devices. One of the reasons is the fact that (LSIs), and thin-film transistors (TFTs) for liquid crystal such silicon nitride films differ from mask materials com displays on glass Substrates, there has been technology well posed mainly of silicon Such as silicon oxide and oxygen in established in which a photoresist is used to form the neces terms of anticorrosion capability. This capability makes Sure sary device structure or circuit structure pattern that is in turn a silicon nitride layer is used as a stopper layer for dry etching, etched in an etching step for removal of unnecessary portions a corrosion preventive layer, a mask or the like in the produc thereby obtaining the desired device structure or circuit struc tion of semiconductor devices. The silicon nitride film may be ture used in combination with a low-dielectric-constant insulating 0003. The device structure or circuit structure to beformed material of the silicon oxide type represented by Low-kmate may have a variety of configurations depending on the desired rial or the like and containing oxygen and other elements such electronic device. In recent years, however, a variety of struc as fluorine and carbon for patterning or acquiring selective tures using silicon nitride film materials have also been under etching capability when they are used as a mask. study. Typically in the process for producing non-volatile 0008. However, a problem with such etching or cleaning memory devices like flash memory devices, a gate insulating steps is that when the etching solution and cleaning Solution film pattern and a gate electrode pattern are formed on a used corrode the aforesaid compounds, the silicon film con semiconductor Substrate. These electrode structures gener taining nitrogen is also more or less corroded. In particular, ally comprise an electrode material that is made conductive recent microstructures of devices are likely to be subject to by incorporating a dopant in polysilicon and an insulating noticeable adverse influences even from a slight corrosion; So film formed of SiO, SiN or SiON. When the electrode struc there is mounting demand for the development of more ture further includes a floating gate and a control gate, there is advanced corrosion preventive technology. an insulating layer formed of ONO (oxide-nitride-oxide), 0009 Translation of PCT Application No. 2004-528716 SiON or SiN so as to insulate them. To this end there is a step goes deep into adverse influences of etch selectivity on Such provided in which the semiconductor substrate is etched materials as silicon oxides in the step of wet etching materials across the gate electrode pattern to form a trench. containing silicon and nitrogen Such as silicon nitride and 0004 For a DRAM memory cell structure too, the struc silicon oxynitride. However, what is considered there is a ture of a silicon nitride film is adopted. Typically in a stack problem with the etching of such a material as silicon oxide at type memory cell, a device isolation area is formed on a the time of etching a material containing silicon and nitrogen, P-type silicon Substrate to form a gate oxide film and a gate and that publication says or suggests nothing about the electrode. Then, a Source? drain area is formed, and an insu reverse phenomenon whatsoever. In addition, the aforesaid lating film is furtherformed by CVD or the like, with a contact problem is only solved by performing etching in a dilute provided on it. Then, there is a polycrystalline silicon film aqueous Solution containing hydrofluoric acid (HF) in a con formed for electric conductivity, which film is in turn pat centration range of 0.001M to 0.1Mata temperature of 25°C. terned to form a lower electrode of a capacitor. Then, a thin to 90°C. In other words, the temperature and concentration of silicon nitride film is formed by CVD all over the surface to the aqueous solution of hydrofluoric acid are nothing else provide the capacitor with an upper electrode. Then, a BPSG than defined. For this reason, any study of prevention of film (insulating film) is formed by CVD, and a contact for corrosions by the introduction of other compound elements is connection to a bit line for data retrieval is opened using not made at all. known photolithographic/etching technology. Finally, an electric conductive film and a BPSG (insulating film) are PRIOR ART formed to obtain a stack type DRAM memory cell. Patent Publication 0005. The silicon nitride film is also used for the formation of a photodiode proximity structure of a conventional CCD (0010 Patent Publication 1 Translation of PCT Applica imaging device including a device isolation mechanism hav tion No. 2004-528716 ing an STI structure. Specifically, a silicon Substrate is pro vided on it with an insulating film comprising a silicon oxide SUMMARY OF THE INVENTION film, and the insulating film is provided on it with a protective film comprising a silicon nitride film or the like. This protec Objects of the Invention tive film is provided on it with a resist pattern having an 0011. The present invention has for its objects to provide opening or aperture in the area having the device isolation an aqueous solution capable of (1) selectively protecting a US 2015/0279.654 A1 Oct. 1, 2015

nitrogen-containing silicon compound from corrosions 4 The treating solution for electronic parts as recited in any caused by chemicals used for various treatments such as one of 1 to 3, wherein said hydrofluoric acid is obtained by etching and cleaning while, at the same time, (2) etching dissolution of a water-soluble fluoride salt. silicon in general, and oxygen-containing, carbon-containing silicon in particular, and (3) making a large difference in etch 5The treating solution for electronic parts as recited in any rate between a nitrogen-containing silicon compound and an one of 1 to 4, which contains a cyclic compound having an oxygen-containing silicon compound, and a process for pro occupied area Smaller than a naphthalene ring. ducing electronic parts using that aqueous solution. 6. The treating solution for electronic parts as recited in 5. wherein said cyclic compound is represented by the following How to Attain the Objects formulae (4), (5), (6) or (7). 0012. The aforesaid objects are achievable by the inven tions embodied as follows. (4) 1 A treating solution for electronic parts, which is an aque ous solution containing one or two or more of anionic Surface active agents having the following formulae (1), (2) and (3).

(1) 10016. In Formula (4), a. a. as a, and as stands for any one or more of a carbon atom, a nitrogen atom, an oxygen a-y atom, a Sulfur atom and a phosphorus atom, wherein these 5 constituting elements form a cyclic structure by having any chemical bond between neighboring constituting elements, O providing a cyclic compound showing aromaticity under con ditions under which it is used. Further, a, a, a3, a and as 0013. In Formula (1), R. R. and R stands for hydrogen may bond to a functional group, or may be a polymer thereof. or an alkyl or alkylene group having 1 to 4 carbonatoms, and X stands for a functional group capable of becoming an anionic ion. (5)

(2) R4 ;: 0017. In Formula (5), b, b. b. b. bs, and be stands for any one or more of a carbonatom, a nitrogenatom, an oxygen CC4\x atom, a Sulfur atom and a phosphorus atom, wherein these 6 X2 pi constituting elements form a cyclic structure by having any chemical bond between neighboring constituting elements, providing a cyclic compound showing aromaticity under con 0014. In Formula (2), R stands for hydrogen oran alkyl or alkylene group having 1 to 4 carbon atoms, X stands for a ditions under which it is used. Further, b, b. bs, babs, and functional group capable of becoming an anionic ion, and in be may bond to a functional group, or may be a polymer stands for a natural number of 2 or greater. thereof.

(6) (3) s N c9- 4 A COA-4 ex c8 s X4 X Y, - c6

0015. In Formula (3), Rs stands for hydrogen oran alkyl or 10018. In Formula (6), c. c2, cs, ca, c. c. c.7, cs, and co alkylene group having 1 to 4 carbon atoms, and X, and X stands for any one or more of a carbonatom, a nitrogenatom, stands for a functional group capable of becoming an anionic an oxygen atom, a Sulfur atom and a phosphorus atom, ion. wherein these 9 constituting elements form a cyclic structure 2 The treating Solution for electronic parts as recited in 1. by having any chemical bond between neighboring constitut wherein said aqueous Solution has a pH value of 2 to 6. ing elements, providing a cyclic compound showing aroma 3 The treating solution for electronic parts as recited in 1 ticity under conditions under which it is used. Further, c. c. or 2, which contains hydrofluoric acid in an amount of 0.001 cs, ca, c. c. c.7, cs, and co may bond to a functional group, or to 50 mass %. may be a polymer thereof. US 2015/0279.654 A1 Oct. 1, 2015

The application of Such a treating solution to etching, clean (7) ing or other treatment(s) of electronic parts makes Sure selec tive prevention of corrosions of nitrogen-containing silicon compounds. If ingredients capable of achieving functions depending on the purpose of electronic parts are added to the present treating solution, it is then possible to use the present treating solution for etching, cleaning or other necessary treatmentS. 0022. The compounds represented by Formula (1) are now 0019. In Formula (7), d, d, d, d, ds, d, d7, and ds stands explained. Formula (1) is representative of a compound hav for any one or more of a carbon atom, a nitrogen atom, an ing a naphthalene skeleton with each benzene ring having oxygen atom, a Sulfur atom and a phosphorus atom, wherein Substituents RandR, and R and X. In Formula (1), R. R. these 8 constituting elements form a cyclic structure by hav and R stands for hydrogen, or an alkyl or alkylene group ing any chemical bond between neighboring constituting ele having 1 to 4 carbon atoms. The alkyl group indicated by R. ments, providing a cyclic compound showing aromaticity R, and R has preferably 1 to 4 carbon atoms, and may be in under conditions under which it is used. Further, d, d, d, d. a straight or branched chain form. Further, the alkyl group ds, d, d7, and ds may bond to a functional group, or may be may further have a substituent(s). Specifically but not exclu a polymer thereof. sively, the alkyl group indicated by R. R. and R includes 7. The treating solution for electronic parts as recited in 5 —CH, —CHCH. —CH2—CH2, —CH(CH), —CH or 6, which contains said cyclic compound in an amount of (CH), and —CH2CH2CH2, among which preference is 0.001 mass % or greater. given to an isopropyl group —CH(CH). R. R. and R may 8The treating solution for electronic parts as recited in any be the same or different from one another. one of 1 to 6, which contains said anionic Surface active 0023 X stands for a functional group that becomes an agent in an amount of 0.001 mass % to 2 mass %. anionic ion. It follows that the compound of Formula (1) 9The treating solution for electronic parts as recited in any functions as an anionic Surface active agent by way of the one of 1 to 8, wherein said aqueous Solution contains a aforesaid hydrophobic groups R to R and the hydrophilic buffer comprising a weak acid and an alkali species. group X. In other words, X is preferably a functional group 10. The treating solution for electronic parts as recited in any capable of functioning as Such a surfactant. Specifically but one of 1 to 9, which further contains an organic solvent not exclusively, preference is given to any one of —SO, miscible with water. –OSO, COO, -P(O).O. —CHSO, and 11 The treating solution for electronic parts as recited in any —CHCOO, among which any one of SO. —OSO or one of 1 to 10, which is used with an electronic part —P(O)O is most preferred. including a structure having a nitrogen-containing silicon 0024 Specific examples of the compound represented by compound as a component material, and a structure having a Formula (1) are naphthalenesulfonic acid, alkyl naphthalene nitrogen-free silicon compound as a component material. Sulfonic acid, sodium alkyl naphthalene Sulfonate, naphtha 12 A process for producing electronic parts, which includes lene carboxylate, 2-methyl-1-naphthalenecarboxylic acid, a step of etching or cleaning an electronic part, using the monoisopropylnaphthalenesulfonic acid, diisopropylnaph treating solution for electronic parts as recited in any one of thalenesulfonic acid, triisopropyl naphthalenesulfonic acid, 1 to 10. dibutyl naphthalenesulfonic acid, etc. 13 The process for producing electronic parts as recited in 0025. The compounds represented by Formula (2) are now 12, in which said electronic part includes a structure having explained. The compound of Formula (2) includes monomers a nitrogen-containing silicon compound as a component having a naphthalene skeleton, wherein they are linked material, and a structure having a nitrogen-free silicon com together by way of CH-” and polymerized. One phenyl pound as a component material. ring of naphthalene includes a Substituent Ra, while another phenyl ring includes a substituent X. The Substituents R and Advantages of the Invention X- are synonymous with the aforesaid R and X. The Small letter n indicative of a number of repetitions stands for a 0020. According to the invention, it is possible to provide natural number of 2 or greater; however, n is usually of the a treating Solution capable of selectively protecting a nitro order 2 to 50 although not limited to it. gen-containing silicon compound from corrosions caused by 0026 Specific examples of the compound represented by chemical Solutions or treating Solutions in general, and a Formula (2) are a naphthalenesulfonic acid/formalin conden chemical Solution containing an acid Such as hydrofluoric sate or the like. acid in particular while, at the same time, etching a nitrogen 0027. The compounds represented by Formula (3) are now free silicon compound containing oxygen and carbon, and explained. The compound of Formula (3) includes a diphenyl making a large difference in etch rates between a nitrogen ether skeleton, wherein the benzene rings each include Sub containing silicon compound and a nitrogen-free silicon com stituents Rs. X and X. The Substituents Ra and X may be pound containing oxygen and carbon, and a process for pro exclusively present in one or both of the benzene rings. The ducing electronic parts using this aqueous solution as well. Substituents Rs. X and X are synonymous with the aforesaid R and X, and X and X may be the same or different from MODE FOR CARRYING OUT THE INVENTION each other. 0021. The treating solution for electronic parts according 0028 Specific examples of the compound represented by to the invention is an aqueous solution that contains one or Formula (3) include an alkyldiphenyl ether sulfonic acid and two or more of the anionic Surface active agents or Surfactants its salt such as alkyldiphenyl ether Sodium Sulfonate and an represented by the aforesaid general formulae (1), (2) and (3). alkyldiphenyl ether sodium disulfonate, a dodecyldiphenyl US 2015/0279.654 A1 Oct. 1, 2015

ether disulfonic acid and its salt such as dodecyldiphenyl thalene. Note here that the “molecular area’ refers to the ether calcium disulfonate, etc. occupied area of a cyclic structure moiety. As the compound 0029. The compounds represented by Formulae (1), (2) having a Smaller occupied area is introduced in the treating and (3) may be used alone or in combination of two or more, Solution, it would be located and arranged on the Surface and or all of them may be used. Among others, the compound of Surroundings of what is to be protected in Such a way as to fill Formula (1) is most preferred; it may be used alone or in up gaps in the compounds of Formulae (1), (2) and (3), combination with other compound(s). contributing more to enhanced protective and anticorrosive 0030. In use, the compounds of the invention represented actions on chemicals. When the aforesaid molecular or occu by Formulae (1), (2) and (3) are added to a treating or pro pied area is unknown, it is preferable to use a compound in cessing solution for electronic devices such as an etching which the number of elements forming a basic skeleton is less Solution, a cleaning solution, and a rinsing Solution. They are than that of naphthalene. Although the coexisting compounds added to it in an amount of 0.001 mass % or greater, prefer of Formulae (1), (2) and (3) may be used for comparing area ably 0.001 to 2 mass %, and more preferably 0.001 to 0.5 size, it is convenient to use naphthalene whose size is gener mass % per the total amount of the treating solution to which ally equal to or Smaller than their size. they are to be added. Too less causes the anticorrosion effect 0035. These compounds should preferably show aroma to get slim, and too much is less cost-effective because the ticity under conditions under which they are used. Note here time taken for rinsing gets longer although it has no or little that the compounds are not always required to have aroma adverse influence on that effect. ticity in themselves; that aromaticity may be developed by 0031. In use, the additives of the invention are added to the changes in the electron State of some or all of the constituting treating solution for electronic devices as described above. elements forming the compounds under conditions under Such a treating solution is preferably an aqueous solution in which they are used. The changes in the electron state may be general and an acidic solution in particular whose pH is less an exergonic process or an endergonic process irrespective of than 7, and preferably less than 6. There is no particular the type of process. There is the general mention of ionization limitation imposed on Such an acidic solution provided that it by dissociation, binding changes by chemical reactions, contains an acid used commonly in the process of producing extraneous light irradiation, electromagnetic wave irradia electronic devices such as semiconductors and liquid crystal tion, application of Voltages, etc. devices. There is the specific mention of an aqueous solution 0036 Further, these compounds may contain hetero atoms containing hydrofluoric acid, hydrochloric acid, phosphoric in their cyclic structure, and the constituting elements of the acid, nitric acid, or a combination of two or more of these cyclic structure may bond to other elements than those form acids, optionally with an aqueous Solution of hydrogen per ing the cyclic structure. To put it another way, the cyclic oxide added to it. The concentration of these acids may be compounds may contain functional groups irrespective of within the known concentration range used for this type treat their type. Even if water solubility become poor by the intro ing solution, and may be selected depending on the functions duction of functional groups, there is likelihood that solubi and performance of the necessary solution. lization may take place by way of the aforesaid compounds 0032 Especially in the invention, preference is given to a (1), (2) and (3). In no event of dissolution, however, may a treating solution used for the treatment of a device including Suitable organic solvent be added. a nitrogen-free, oxygen-containing silicon compound and a 0037. These compounds may be polymerized via any nitrogen-containing silicon compound now that the invention functional elements or functional groups on their molecular has a specific feature of having a high etch ratio for both the structure. It is here to be noted that the polymer is not neces compounds. Such a treating solution is preferably an aqueous sarily formed already at the time of solution formulation; it Solution containing hydrofluoric acid in an amount of prefer may be formed by way of any chemical reaction after formu ably 0.001 to 50 mass %, and more preferably 0.01 to 20 mass lation, or before or during use. The “any chemical reaction' %. here refers to dehydration condensation, electrolytic poly 0033 Although hydrofluoric acid may be added to the merization or the like regardless of the type of chemical treating solution in the form of hydrogen fluoride, it is pref reaction. That chemical reaction may be either an exergonic erable to use hydrofluoric acid by itself. There may be water process or an endergonic process. soluble fluoride salts or the like used, among which ammo 0038 Although there is no particular limitation on such nium fluoride is most preferred. Instead of the ammonium cyclic compounds with the proviso that they satisfy the afore fluoride that is usually a salt represented by NHF, it is pos said conditions, it is preferable to use a five-membered ring sible to use ammonium hydrogen fluoride represented by compound alone, a six-membered ring compound alone, a (NH4)HF. Usually, as ammonium fluoride is dissolved in the five-membered ring compound condensed with a four-mem treating solution, it will cause the treating solution to contain bered ring compound, and a five-membered ring compound hydrofluoric acid, ammonium ions and ammonia derived condensed with a six-membered ring compound, and particu from it in equimolecular amounts. The content of ammonium lar preference is given to a compound having an indan skel fluoride is preferably 0.00185 to 40 mass %, and more pref eton as represented by Formula (6) or a compound repre erably 0.00185 to 37 mass %. Further, hydrofluoric acid may sented by Formula (4). Optionally, it is also possible to use a be added alone or in combination with other additive(s) in compound having five-membered ring compounds combined Such a way as to become excessive. with each other. 0034. In addition to the anionic surfactants represented by 0039 Referring to the cyclic compound of Formula (4), the aforesaid Formulae (1), (2) and (3), it is herein preferable the constituting elementa, a2, as a, and as stands for at least for the treating Solution to contain a molecule having an one of carbon, nitrogen, oxygen, Sulfur and phosphorus occupied area Smaller than those of Formulae (1), (2) and (3), atoms, and these elements provide the respective constituting i.e., a cyclic compound in which the occupied area of a cyclic elements alone or in combination of two or more. The respec structure moiety is Smaller than the molecular area of naph tive constituting elements may be the same or different from US 2015/0279.654 A1 Oct. 1, 2015

each other. These five constituting elements include chemical ole derivatives, triazole adducts of pyrimidine derivatives, bonds between neighboring constituting elements. Note here triazolylpyridazine, pyridazine adducts of triazole deriva that the types of chemical bonds do not matter. Further, a, a tives, triazole adducts of pyridazine derivatives, tetrazole, as a, and as may further bond to a functional group regard tetrazolyl salts, tetrazole derivatives, phenyltetrazole, tetra less of the type of functional group. This compound forms a Zole adducts of benzene derivatives, benzene adducts of tet cyclic structure by way of the aforesaid five constituting razole derivatives, tetrazolyl-pyridine, pyridine adducts of elements. tetrazole derivatives, tetrazole adducts of pyridine deriva 0040. The cyclic compound of Formula (4) shows aroma tives, tetrazolyl-triazine, triazine adducts of tetrazole deriva ticity under conditions under which it is used. The conditions tives, tetrazole adducts of triazine derivatives, tetrazolylpyri under which this compound takes on aromaticity would midine, pyrimidine adducts of tetrazole derivatives, tetrazole appear to include, in addition to the aromaticity that this adducts of pyrimidine derivatives, tetrazolylpyridazine, compound has in itself, ionization and radicalization of the pyridazine adducts of tetrazole derivatives, tetrazole adducts elements (atoms)a, a2, as a and as changes in the bond type of pyridazine derivatives, pentazole, pentazolyl salts, penta of the elements (atoms) a, a2, as a and as detachment of Zole derivatives, phenylpentazole, pentazole adducts of ben atoms or functional groups attached to the elements (atoms) Zene derivatives, benzene adducts of pentazole derivatives, a1, a2, as a and as changes in the bond type of atoms or pentazolylpyridine, pyridine adducts of pentazole deriva functional groups attached to the elements (atoms) a, a, as tives, pentazole adducts of pyridine derivatives, pentazolyl a and as ionization and radicalization of atoms attached to triazine, triazine adducts of pentazole derivatives, pentazole the elements (atoms) a. a. as a and as ionization and adducts of triazine derivatives, pentazolylpyrimidine, pyrimi radicalization of functional groups attached to the elements dine adducts of pentazole derivatives, pentazole adducts of (atoms) a, a2, as a and as chemical changes such as oxi pyrimidine derivatives, pentazolylpyridazine, pyridazine dization and reduction of functional groups attached to the adducts of pentazole derivatives, pentazole adducts of elements (atoms) a, a2, as a and as and extraneous light pyridazine derivatives, furan, furan derivatives, phenylfuran, irradiation, electromagnetic wave irradiation, application of furan adducts of benzene derivatives, benzene adducts of Voltages, etc. It is here to be noted that the type of, and process furan derivatives, furanylpyridine, pyridine adducts of furan of development of aromaticity does not matter. derivatives, furan adducts of pyridine derivatives, furanyltri 0041. The cyclic compounds represented by Formula (4) azine, triazine adducts of furan derivatives, furan adducts of include pyrrole, pyrryl salts, pyrrole derivatives, phenylpyr triazine derivatives, furanylpyrimidine, pyrimidine adducts role, pyrrole adducts of benzene derivatives, benzene pyrrole of furan derivatives, furan adducts of pyrimidine derivatives, derivative adducts, pyrrolylpridine, pyrrolylpyrimidine, pyr furanylpyridazine, pyridazine adducts of furan derivatives, rolylpyridazine, pyrrolyltriazine, pyridine pyrrole derivative furan adducts of pyridazine derivatives, thiophene, thiophene adducts, pyrimidine pyrrole derivative adducts, pyridazine derivatives, phenyl-thiophene, thiophene adducts of benzene pyrrole derivative adducts, triazole pyrrole derivative derivatives, benzene adducts of thiophene derivatives, adducts, pyrrole pyridine derivative adducts, pyrrole triazine thiophenyl-pyridine, pyridine adducts of thiophene deriva derivative adducts, pyrrole pyrimidine derivative adducts, tives, thiophene adducts of pyridine derivatives, thiophenyl pyrrole pyridazine derivative adducts, pyrrole triazine deriva triazine, triazine adducts of thiophene derivatives, thiophene tive adducts, pyrazole, pyrazolyl salts, pyrazole derivatives, adducts of triazine derivatives, thiophenyl-pyrimidine, pyri phenyl-pyrazole, pyrazole adducts of benzene derivatives, midine adducts of thiophene derivatives, thiophene adducts benzene adducts of pyrazole derivatives, pyrazolyl-pyridine, of pyrimidine derivatives, thiophenyl-pyridazine, pyridazine pyridine adducts of pyrazole derivatives, pyrazole adducts of adducts of thiophene derivatives, thiophene adducts of pyridine derivatives, pyrazolyl-triazine, triazine adducts of pyridazine derivatives, thiophene polymers, oxazole, oxazole pyrazole derivatives, pyrazole adducts of triazine derivatives, derivatives, phenyloxazole, oxazole adducts of benzene pyrazolyl-pyrimidine, pyrimidine adducts of pyrazole deriva derivatives, benzene adducts of oxazole derivatives, tives, pyrazole adducts of pyrimidine derivatives, pyrazolyl oxazolylpyridine, pyridine adducts of oxazole derivatives, pyridazine, pyridazine adducts of pyrazole derivatives, pyra oxazole adducts of pyridine derivatives, oxazolyltriazine, tri Zole adducts of pyridazine derivatives, imidazole, imidazolyl azine adducts of oxazole derivatives, oxazole adducts of tri salts, imidazole derivatives, phenylimidazole, imidazole azine derivatives, oxazolylpyrimidine, pyrimidine adducts of adducts of benzene derivatives, benzene adducts of imidazole oxazole derivatives, oxazole adducts of pyrimidine deriva derivatives, imidazolylpyridine, pyridine adducts of imida tives, oxazolylpyridazine, pyridazine adducts of oxazole Zole derivatives, imidazole adducts of pyrimidine derivatives, derivatives, oxazole adducts of pyridazine derivatives, thiaz imidazolylpyridine, pyridine adducts of imidazole deriva ole, thiazole derivatives, phenyl-thiazole, thiazole adducts of tives, imidazole adducts of pyridine derivatives, imidazolyl benzene derivatives, benzene adducts of thiazole derivatives, triazine, triazine adducts of imidazole derivatives, imidazole thiazolyl-pyridine, pyridine adducts of thiazole derivatives, adducts of triazine derivatives, imidazolylpyrimidine, pyri thiazole adducts of pyridine derivatives, thiazolyl-triazine, midine adducts of imidazole derivatives, imidazole adducts triazine adducts of thiazole derivatives, thiazole adducts of of pyrimidine derivatives, imidazolylpyridazine, pyridazine triazine derivatives, thiazolyl-pyrimidine, pyrimidine adducts of imidazole derivatives, imidazole adducts of adducts of thiazole derivatives, thiazole adducts of pyrimi pyridazine derivatives, triazole, triazolyl salts, triazole dine derivatives, thiazolyl-pyridazine, pyridazine adducts of derivatives, phenyltriazole, triazole adducts of benzene thiazole derivatives, thiazole adducts of pyridazine deriva derivatives, benzene adducts of triazole derivatives, triaz tives, oxadiazole, oxadiazole derivatives, phyenyloxadiazole, olylpyridine, pyridine adducts of triazole derivatives, triazole oxadiazole adducts of benzene derivatives, benzene adducts adducts of pyridine derivatives, triazolyltriazine, triazine of oxadiazole derivatives, oxadiazolylpyridine, pyridine adducts of triazole derivatives, triazole adducts of triazine adducts of oxadiazole derivatives, oxadiazole adducts of pyri derivatives, triazolylpyrimidine, pyrimidine adducts of triaz dine derivatives, oxadiazolyltriazine, triazine adducts of oxa US 2015/0279.654 A1 Oct. 1, 2015

diazole derivatives, oxadiazole adducts of triazine deriva -continued tives, oxadiazolylpyrimidine, pyrimidine adducts of (I-A9) oxadiazole derivatives, oxadiazole adducts of pyrimidine derivatives, oxadiazolylpyridazine, pyridazine adducts of /S / \ oxadiazole derivatives, oxadiazole adducts of pyridazine \2\ / derivatives, etc., and there is the specific mention of 1H-imi pyrrolylpyridazine dazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimeth (I-A10) ylimidazole, 2-phenylimidazole, 1H-pyrazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3,4-tetrazole, 5-phenyltetrazole, imidazo line, histidine, terthiophene, polythiophene or the like. 0042. By way of example but not by way of limitation, pyrrolyltriazine typical specific structures of the above-exemplified cyclic (I-A11) compounds of Formula (4) are given below.

H (I-A1) pyridine pyrrole derivative adducts r (I-A12) pyrrole

(I-A2) H

AS pyrimidine pyrrole pyrryl salts derivative adducts (I-A13) R (I-A3)

1. H

pyrrole derivatives pyridazine pyrrole derivative adducts (I-A4) (I-A14) R IO-( ) /ss 7N \ phenylpyrrole \4 N / (I-A5) triazole pyrrole derivative adducts (I-A15)

pyrrole adducts of benezene derivatives /N / -\, (I-A6) \4 N / pyrrole triazine derivative adducts n(i. y (I-A16) Ms R benzene pyrrole derivative adducts - V (I-A7) C

HN o N pyrrole pyrimidine derivative adducts (I-A17) pyrrolylpyridine N HN s / \M (I-A8) C HN o N Ms \-/ pyrrole pyridazine pyrrolylpyrimidine derivative adducts US 2015/0279.654 A1 Oct. 1, 2015

-continued -continued (I-B1) (I-B11) " N ) R pyrazole Na Y / (I-B2) triazine adducts of N1 N pyrazole derivatives (I-B12) pyrazolyl salts (I-B3) HN

pyrazole adducts of triazine derivatives pyrazole derivatives (I-B13) (I-B4) HNN2 \ / pyrazolylpyrimidine phenylpyrazole (I-B14) (I-B5) R /Ss / X,W R s N Ya \ . Na \ / pyrazole adducts of pyrimidine adducts of benezene derivatives pyrazole derivatives (I-B6) (I-B15) R N N - V.o N benzene adducts of pyrazole adducts of pyrazole derivatives pyrimidine derivatives (I-B7) ^S / \ (I-B16) Na \ / HNN2 \ / pyrazolylpyridine pyrazolylpyridazine (I-B8) (I-B17) HNN2 \ /N pyridine adducts of pyrazole derivatives pyridazine adducts of pyrazole derivatives (I-B9) (I-B18)

HN

pyrazole adducts of pyridine derivatives pyrazole adducts of pyridazine derivatives (I-B10) (I-C) HN

pyrazolyltriazine imidazole US 2015/0279.654 A1 Oct. 1, 2015

-continued -continued (I-C1) (I-C10) 1n N H R M imidazolyl salts K" ( ), (I-C2) triazine adducts of imidazole derivatives (I-C11)

imidazole derivatives (I-C3) H kid'),\ l \ =/ N imidazole adducts of triazine derivatives {N l phenylimidazole (I-C12) (I-C4) R J N / {3 / 3 imidazolylpyrimidine (I-C13) imidazole adducts of benzene derivatives N.H f N (I-C5) (KYN- \-/\- pyrimidine adducts of imidazole derivatives (I-C14) benzene adducts of imidazole derivatives (I-C6) l \ / imidazole adducts of pyrimidine derivatives imidazolylpyridine (I-C15) (I-C7) { J N/ R./ imidazolylpyridazine NN l \ o/ pyridine adducts of (I-C16) imidazole derivatives (I-C8)

pyridazine adducts of - \ / imidazole derivatives (I-C17) imidazole adducts of pyridine derivatives (I-C9)

imidazole adducts of pyridazine derivatives imidazolyltriazine US 2015/0279.654 A1 Oct. 1, 2015

-continued -continued (I-D1) (I-D10) N HN N-H f N / ) A \ \- N Y= / (I-D2) triazine adducts of N triazole derivatives / Sa N NN (I-D11) R \ / or H triazolyl salts y) MN f\, (I-D3) N. R HN1 X triazole adducts of triazine derivatives O RN triazole derivatives (I-D12) (I-D4) N V / triazolylpyrimidine O phenyltriazole (I-D13) H R N (I-D5) H // / \ R N R /S / x N/N / X NT V / N o O pyrimidine adducts of triazole derivatives triazole adducts of benzene derivatives (I-D14) (I-D6) N/ NYu M benzene adducts of triazole derivatives triazole adducts of pyrimidine derivatives (I-D6) (I-D15) N N N? / \ N? N / \ \l V / \ l o O \- N o triazolylpyridazine (I-D7) (I-D16) Nil / \ R

pyridine adducts of triazole derivatives pyridazine adducts of triazole derivatives (I-D8) (I-D17)

N MN in A f\N y) / \ s / \, Y- \ / or N N Yu =\/ N-N -A/ triazole adducts of pyridine derivatives (I-D9) triazole adducts of pyridazine derivatives

N N

triazolyltriazine tetrazole US 2015/0279.654 A1 Oct. 1, 2015 10

-continued -continued (I-E2) (I-E11) N N1/S N H R K.N Y. tetrazolyl salts (I-E3) triazine adducts of NR tetrazole derivatives 1 >S HN N (I-E12) R \=l H RN N N tetrazole derivatives N if \ M V N (I-E4) N- N N=/ N NN tetrazole adducts of N triazine derivatives N-N (I-E13) phenyltetrazole

s W R

NT (I-E14) tetrazole adducts of benzene derivatives

pyrimidine adducts of tetrazole derivatives (I-E15) benzene adducts of tetrazole derivatives M N (I-E7) N-N \=/ tetrazole adducts of pyrimidine derivatives (I-E16) N (I-E8) N & - N (\ )M N tetrazolylpyridazine (I-E17) pyridine adducts of tetrazole derivatives

pyridazine adducts of tetrazole derivatives (I-E18) tetrazole adducts of pyridine derivatives ki / R.N (I-E10) N' \--/

tetrazole adducts of pyridazine derivatives tetrazolyltriazine US 2015/0279.654 A1 Oct 1, 2015 11

-continued -continued (I-F1) (I-F10) N HN1SN V / NRN pentazole (I-F2) N N1SN/ (I-F11) V / NRN pentazolyl salts (I-F3) R triazine adducts of HN1%NN pentazole derivatives V / NRN pentazole derivatives (I-F12) (I-F4) H N

pentazole adducts of phenylpentazole triazine derivatives (I-F5) (I-F13)

pentazole adducts of benzene derivatives (I-F6) (I-F14) H R N. N RN \ -N benzene adducts of pyrimidine adducts of pentazole derivatives pentazole derivatives (I-F15) (I-F7) /NNN-H NTVf N N N-N \=/ pentazole adducts of pyrimidine derivatives (I-F8) (I-F16)

pyridine adducts of pentazole derivatives pentazolylpyridazine (I-F9) (I-F17) /-Ntf / NV

pentazole adducts of pyridazine adducts of pyridine derivatives pentazole derivatives US 2015/0279.654 A1 Oct. 1, 2015 12

-continued -continued H (I-F18) O N V (I-G8) NN N N / \

YN A \, { } { o N \ -N \ =\=/ N R furanyltriazine pentazole adducts of R (I-G9) pyridazine derivatives O N (I-G) {{ \

triazine adducts of f furan derivatives 8. R (I-G10) (I-G1) 1SSR O in /N \ ( ) Nu Y / furan derivatives furan adducts of (I-G2) triazine derivatives

N O N (I-G11) {C-(phenylfuran ) KC-(\-/ ) furanylpyrimidine (I-G3) O R (I-G12) o in A \ furan adducts of N \-/ benzene derivatives pyrimidine adducts of (I-G4) furan derivatives R O.f (I-G13) {3 ') / f\,R benzene adducts of N \-/ furan derivatives furan adducts of (I-G5) pyrimidine derivatives CinNJ A \, O a / N\, (I-G14) furanylpyridine N M/ (I-G6) furanylpyridazine of / \ R (I-G15) (3 ( ) 9| 7 R. pyridine adducts of \ J V NR / furan derivatives pyridazine adducts of (I-G7) furan derivatives (I-G16) in A \, {3'S \-\// \, furan adducts of pyridine derivatives furan adducts of pyridazine derivatives US 2015/0279.654 A1 Oct. 1, 2015 13

-continued -continued (I-H10) R () S thiophene triazine adducts of (I-H1) thiophene derivatives (I-H11) thiophene derivatives (3°)S. Z \, thiophene adducts of triazine derivatives (I-H2) (I-H12)

phenylthiophene thiophenylpyrimidine (I-H4) (I-H13) R S. /N \ thiophene adducts of N benzene derivatives pyrimidine adducts of (I-H5) thiophene derivatives R (I-H14) (3-(S f ) R benzene adducts of thiophene derivatives thiophene adducts of pyrimidine derivatives N}( / ) (I-H15) thiophenylpyridine thiophenylpyridazine (I-H7) R (I-H16) S R N N (3-)in A \, pyridine adducts of thiophene derivatives pyridazine adducts of thiophene derivatives (I-H8) (I-H17) S N / R o N N N thiophene adducts of thiophene adducts of pyridine derivatives pyridazine derivatives C(i) (I-H9) (I-H18) thiophenyltriazine terthiophene US 2015/0279.654 A1 Oct. 1, 2015 14

-continued -continued (I-H19) O N N (I-I9)

{ / \, /ho M \, k N- Y=/ O Null Y=/ polythiophene oxazolyltriazine (I-I10) (I-1)

oxazole triazine adducts of oxazole derivatives (I-I1) (I-I11) R NSR SN o1 \ f O Kid'), /h /jiv oxazole derivatives NJ Y=/ O Null Y=/ oxazole adducts of triazine derivatives (I-I12) (NJ ( ) O {Null phenyloxazole -TV / Nu \ (I-I3) oxazolylpyrimidine O R (I-I13) K.N- \ /s." or \ll^ \M. X. R N R oxazole adducts of benzene derivatives { } {4. \, /* in 7 \, N o O Null

R O //O (I-I14) {3 O NNu benzene adducts of oxazole derivatives J N / NJ (I-I5) (I-I15) N O oxazolylpyridine - \ / or

(I-I16) N O pyridine adducts of oxazole derivatives l Y=/ O

R f (I-I17) N 4 N (o\ ) O X o pyridine adducts of oxazole derivatives R O R

/ N o N / v N N C) O oxazole adducts of pyridine derivatives

US 2015/0279.654 A1 Oct. 1, 2015 16

-continued -continued (I-K3) (I-K12) R //N NNull NJ V / benzene adducts of oxadiazole adducts of oxadiazole derivatives pyrimidine derivatives (I-K4) (I-K13) OS /NNJ V/ \/ oxadiazolylpyridine oxadiazolylpyridazine (I-K5) (I-K14) 'NR / \, \- \/ pyridine adducts of pyridazine adducts of oxadiazole derivatives oxadiazole derivatives (I-K6) (I-K15) /SNNJ V/ \/ oxadiazole adducts of oxadiazole adducts of pyridine derivatives pyridazine derivatives (I-K7) 0043 Referring to the cyclic compounds of Formula (5), N o N the constituting element b,b,b,b,bs, and be stands for at N least one of carbon, nitrogen, oxygen, Sulfur, and phosphorus atoms. Usually, these elements provide the respective consti oxadiazolyltriazine tuting elements by themselves, but they may be applied in (I-K8) combination of two or more. These six constituting elements R include a chemical bond between neighboring constituting elements regardless of the type of bond. Otherwise, the same N as the abovementioned a1, a2, as aa, and as will hold true. 0044) The cyclic compounds of Formula (5), too, show triazine adducts of aromaticity under conditions under which they are used, as is oxadiazole derivatives the case with the aforesaid compounds of Formula (4). As is (I-K9) again the case with the aforesaid compound of Formula (4), R the conditions for this compound to show aromaticity would ps N Alv appear to include, in addition to the fact that it possesses N o N aromaticity in itself, ionization or radicalization of the ele ments (atoms) b,b,b,b,bs and be changes in the type of bond of the elements b, b. b. b. bs and be detachment of oxadiazole adducts of atoms or functional groups attached to the elements b,b,b, triazine derivatives babs and be changes in the type of bond of atoms or func (I-K10) tional groups attached to the elements b,b,b,b,bs and be ionization or radicalization of atoms attached to elements at o N / \, the 1 to 6 positions, oxidization or reduction of functional NJ V / groups attached to the elements b, b. bs, b. bs and be extraneous light irradiation, electromagnetic wave irradia oxadiazolylpyrimidine tion, application of voltages, etc., and so on. Note here that the (I-K11) type of, and the process of development of aromaticity does not matter. 0045. The cyclic compounds represented by Formula (5) include pyridine, pyridinium salts, pyridine derivatives, pyridazine, pyridazine derivatives, pyrimidine, pyrimidine pyrimidine adducts of derivatives, pyrazine, pyrazine derivatives, triazine, triazine oxadiazole derivatives derivatives, tetrazine, tetrazine derivatives, pyran, pyran derivatives, dioxin, dioxin derivatives, thiopyran, thiopyran US 2015/0279.654 A1 Oct. 1, 2015

derivatives, dithiin, dithin derivatives, oxathiin, oxathiin 1,4-dithiin-2-carboxylic acid, 1,4-dithiin-2,3-dicarboxylic derivatives, benzene derivatives, aniline, aniline derivatives, acid, 2,6-diphenyl-1,4-dithin, 2,5-diphenyl-1,4-dithiin, benzoic acid, benzoic acid derivatives, phthalic acid, phthalic dithiin-4-carboxylic acid, dithiin-3,4-dicarboxylic acid, acid derivatives, phenol, phenol derivatives, polyvalent phe dithiin-3,6-diamine, dithin-4,5-diol. 3,6-diphenyldithiin, nol, polyvalent phenol derivatives, flavan, flavonoid, Vanil 2-vinyl-4H-1,3-dithiin, oxathiin-3-carboxylic acid, oxathiin loid, etc. There is the specific mention of pyridine, pyridazine, 3,4-diamine, 6-phenyloxathiin, 3,4-diphenyloxathin, 1.4- pyrimidine, pyrazine, 1,2,3-triazine, 1.2-4-triazine, 1,3,5-tri Oxathiin-2-carboxylic acid, 2-methyl-1,4-oxathiin, 3-me azine, 1,2,3,4-tetrazine, 1,2,4,5-tetrazine, 1,2,3,5-tetrazine, thyl-1,4-oxathiin, 2-phenyl-1,4-oxathiin, 3-phenyl-1,4- 2H-pyran, 1,4-dioxin, 1,2-dioxin, 4H-1,3-dioxin, 2H-thiopy Oxathiin, 2,3-diphenyl-1,4-oxathiin, flavone, catechin, ran, 1,4-dithiin, 1,2-dithiin, 4H-1,3-dithiin, 1.2-oxathiin, 1,4- vanillin, vanillic acid, ferulic acid, ethylvanillin, 2,3-dihy Oxathiin, 4H-1,3-oxathiin, benzoic acid, nicotinic acid, isoni droxybenzoic acid, 2,4-dihydroxy Zenzoic acid, 2,5-dihy cotinic acid, pyridine-3-amine, pyridine-4-amine, pyridin-3- droxyZenoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihy ol, pyridin-4-ol. 3-phenylpyridine, 4-phenylpyridine, droxybenzoic acid,3,5-dihydroxybenzoic acid, phthalic acid, pyridine fluoride, pyridazine-4-carboxylic acid, pyridazine isophthalic acid, terephthalic acid, benzene-1,3,5-triacetic 3-carboxylic acid, pyridazine-4-amine, pyridazine-3-amine, acid, benzene-1,2,4-triacetic acid, benzene-1,2,3-triacetic pyridaZin-4-ol, pyridazin-3-ol, 3-phenylpyridazine, 4-phe acid, benzaldehyde, nitrobenzene, methyl-2-hydroxybenzoic nylpyridazine, pyrimidine-4-carboxylic acid, pyrimidine-5- acid, 2-hydroxybenzoic acid, phenyl acetate, 4-aminoben carboxylic acid, pyrimidine-4-amine, pyrimidine-5-amine, Zentiol, benzenesulfonic acid, 4-(4-aminophenyl)disulfany pyrimidin-4-ol, pyrimidin-5-ol, 4-phenylpyrimidine, 5-phe laniline, phenylacetamide, acetylsalicylic acid, picric acid, nylpyrimidine, pyrazine-2-carboxylic acid, pyrazine-2,6-di carboxylic acid, pyrazine-2-amine, pyrazine-2,6-diamine, aniline, benzene-1,2-diamine, benzene-1,4-diamine, ben pyrazin-2-ol, pyrazine-2,6-diol. 2-phenylpyrazine, triazine Zene-1,3-diamine, benzene-1,3,5-triamine, benzene-1,2,4- 4-carboxylic acid, triazine-5-carboxylic acid, triazine-5- triamine, benzene-1,2,3-triamine, phenol, benzene-1,2-diol. amine, triazine-4-amine, triazin-5-ol, triazin-4-ol. 5-phenyl benzene-1,4-diol, benzene-1,3-diol, benzene-1,3,5-triol, triazine, 4-phenyltriazine, 1,2,4-triazine-3-carboxylic acid, benzene-1,2,4-triol, benzene-1,2,3-triol, 2-aminophenol, 1,2,4-triazine-6-carboxylic acid, 1,2,4-triazine-5-carboxylic 4-aminophenol, 3-aminophenol, phenylalanine, tyrosine, etc. acid, 1,2,4-triazine-3-amine, 1,2,4-triazine-6-amine, 1,2,4- 0046 By way of example but not by way of limitation, triazine-5-amine, 1,2,4-triazin-3-ol, 1,2,4-triazin-6-ol. 1,2,4- typical specific structures of the above-exemplified cyclic triazin-5-ol. 3-phenyl-1,2,4-triazine, 6-phenyl-1,2,4-triazine, compounds represented by formula (5) are given below. 5-phenyl-1,2,4-triazine, 1,3,5-triazine-2-carboxylic acid, 1,3,5-triazine-2,4-dicarboxylic acid, 1,3,5-triazine-2,4,6-tri acetic acid, 1.3.5-triazine-2-amine, 1,3,5-triazine-2,4-di (II-A) amine, 1,3,5-triazin-2-ol. 1,3,5-triazine-2,4-diol. 2-phenyl-1, N 3,5-triazine, 2,4-diphenyl-1,3,5-triazine, 2,4,6-triphenyl-1,3, n 5-triazine, tetrazine-5-amine, tetrazine-5,6-diamine, tetraZin 5-ol. 5-phenyltetrazine, 5,6-diphenyltetrazine, 1,2,4,5- 21 tetrazine-3-carboxylic acid, 1,2,4,5-tetrazine-3,6- pyridine dicarboxylic acid, 1,2,4,5-tetrazine-3-amine, 1,2,4,5- tetrazine-3,6-diamine, 1,2,4,5-tetrazin-3-ol, 1,2,4,5- N (II-A1) tetrazine-3,6-diol, 3-phenyl-1,2,4,5-tetrazine, 3,6-diphenyl n 1,2,4,5-tetrazine, 1,2,3,5-tetrazine-4-carboxylic acid, 1.2.3, N 5-tetrazine-4,6-dicarboxylic acid, 1,2,3,5-tetrazine-4-amine, 21 1,2,3,5-tetrazine-4,6-diamine, 1,2,3,5-tetrazin-4-ol, 1,2,3,5- tetrazine-4,6-diol, 4-phenyl-1,2,3,5-tetrazine, 4,6-diphenyl pyridinium salts, 1,2,3,5-tetrazine, 2H-pyran-2-carboxylic acid, 2H-pyran-3- pyridine derivatives carboxylic acid, 2H-pyran-4-carboxylic acid, 2H-pyran-2,6- (II-A2) dicarboxylic acid, 2H-pyran-3,5-dicarboxylic acid, N O 2H-pyran-2-amine, 2H-pyran-3-amine, 2H-pyran-4-amine, 2H-pyran-2,6-diamine, 2H-pyran-3,5-diamine, 2H-pyran-2- ol. 2H-pyran-3-ol, 2H-pyran-4-ol. 2H-pyran-2,6-diol. () { 2H-pyran-3,5-diol, 2-phenyl-2H-pyran, 3-phenyl-2H-pyran, nicotinic acid 4-phenyl-2H-pyran, 2,6-diphenyl-2H-pyran, 3,5-diphenyl (II-A3) 2H-pyran, 1.4-dioxin-2-carboxylic acid, 1,4-dioxin-2,3-di O carboxylic acid, 1,4-dioxin-2,6-dicarboxylic acid, 1,4-di oxin-2-amine, 1,4-dioxin-2,3-diamine, 1,4-dioxin-2,6- ()o {OH diamine, 1,4-dioxin-2-ol. 1,4-dioxin-2,3-diol, 1,4-dioxin-2, 6-diol, 2-phenyl-1,4-dioxin, 2,3-diphenyl-1,4-dioxin, isonicotinic acid dioxin-3-carboxylic acid, dioxin-4-carboxylic acid, dioxin 3-ol, 4H-1,3-dioxin-5-amine, 4H-1,3-dioxin-5-ol, 4-phenyl (II-A4) 4H-1,3-dioxin, 2H-thiopyran-3-carboxylic acid, 2H-thiopy ran-4-carboxylic acid, 2H-thiopyran-6-amine, 2H-thiopyran 5,6-diamine, 2H-thiopyran-4-amine, 2H-thiopyran-6-ol. 2H-thiopyran-3-ol, 2H-thiopyran-4-ol. 2H-thiopyran-4- pyridine-3-amine thiol, 3-phenyl-2H-thiopyran, 2,6-diphenyl-2H-thiopyran, US 2015/0279.654 A1 Oct. 1, 2015 18

-continued -continued (II-A5) (II-B5) NN

pyridine-4-amine pyridazine-3-amine (II-A6) (II-B6) (N )—on pyridin-3-ol pyridaZin-4-ol (II-A7) (II-B7) (NN ) or pyridin-4-ol pyridazin-3-ol (II-A8) () ( ) () ( ) (II-B8) 3-phenylpyridine 3-phenylpyridazine (II-A9) (II-B9) ( )-( ) (N )-( ) 4-phenylpyridine 4-phenylpyridazine (II-A10) N (II-C) 21 N F N r2N pyridine fluoride pyrimidine (II-B) (II-C1) N N 2 pyridazine (II-B1) (II-C2) NSN > pyridazine derivatives pyrimidine-4-carboxylic acid (II-B2) (II-C3) N O O

o OH / OH pyridazine-4-carboxylic acid pyrimidine-5-carboxylic acid (II-B3) (II-C4)

pyridazine-3-carboxylic acid pyrimidine-4-amine (II-B4) (II-C5) N N & / NH2 pyridazine-4-amine pyrimidine-5-amine

US 2015/0279.654 A1 Oct. 1, 2015 20

-continued -continued (II-E7) (II-E-17) /=N N NH2 V / triazin-4-ol 1,2,4-triazine-5-amine (II-E8) (II-E-18) N N

V NR ()-- 5-phenyltriazine 1,2,4-triazin-3-ol (II-E9) (II-E19) N-N N

() ( ) NRN 4-phenyltriazine 1,2,4-triazin-6-ol (II-E10) (II-E20) N /=N N OH r V N e / 1,2,4-triazine 1,2,4-triazin-5-ol (II-E21) C. (II-E11) &NN 2 3-phenyl-1,2,4-triazine 1,2,4-triazine derivatives (II-E22) (II-E12) NN O ( ) & N OH 6-phenyl-1,2,4-triazine 1,2,4-triazine-3-carboxylic acid (II-E23) (II-E13)

NN OH 5-phenyl-1,2,4-triazine 1,2,4-triazine-6-carboxylic acid (II-E30) (II-E14) Ns Ne N 1,3,5-triazine 1,2,4-triazine-5-carboxylic acid (II-E31) (II-E15) N N 1), Ne-N 1,2,4-triazine-3-amine 1,3,5-triazine derivatives (II-E32) ( ) is (II-E16) { } {OH 1,2,4-triazine-6-amine 1,3,5-triazine-2-carboxylic acid US 2015/0279.654 A1 Oct. 1, 2015 21

-continued -continued (II-E33) OH O (II-F)

N O N OH NeN 1,3,5-triazine-2,4-dicarboxylic acid (II-F1) (II-E34) OH O

N O n OH

N 2 N 1,2,3,4-tetrazine derivatives (II-F2) NN HO O \ NH V 2 1,3,5-triazine-2,4,6-triacetic acid / (II-E35) tetrazine-5-amine / N (II-F3) ( )- N NH2 1,3,5-triazine-2-amine Nin s C NH2 (II-E37) / N tetrazine-5,6-diamine (II-F4) ( )—o NN M N OH 1,3,5-triazin-2-ol V (II-E38) N HO N OH tetrazin-5-ol s (II-F5) N2 N NN 1,3,5-triazine-2,4-diol (II-E39) N '()\ / ( ) / \ 5-phenyltetrazine \=N (II-F6) 2-phenyl-1,3,5-triazine (II-E40)

n Ne O 2,4-diphenyl-1,3,5-triazine 5,6-diphenyltetrazine (II-E41) (II-F10) Ns NNse CO 1,2,4,5-tetrazine (II-F11)

2,4,6-triphenyl-1,3,5-triazine 1,2,4,5-tetrazine derivatives

US 2015/0279.654 A1 Oct. 1, 2015

-continued -continued (II-K) (II-L4) O

O O N1

O

flavonoid, flavan elnythvlvanilli Ivan III in (II-M) (II-K1) O O C’s benzoic acid (II-M1) O O flavone (II-K2) N OH O HO ex O O OH O benzoic acid derivatives (II-M2) O O O O O catechin (II-L) O OH 2,3-dihydroxybenzoic acid O (II-M3) O O R O vanilloid O O (II-L1) 2,4-dihydroxybenzoic acid (II-M4) O O O

O vanillin O (II-L2) O O 2,5-dihydroxybenzoic acid (II-M5) O O O O O vanillic acid O (II-L3) O O 2,6-dihydroxybenzoic acid O (II-M6) O O O

O O O ferulic acid 3,4-dihydroxybenzoic acid US 2015/02796.54 A1 Oct. 1, 2015 28

-continued -continued (II-M7) (II-M16) O O /

O benzene derivatives, benzaldehyde O (II-M17) O 3,5-dihydroxybenzoic acid A. N+ (II-M10) V O O nitrobenzene OH (II-M18) O O

OH phthalic acid C OH (II-M11) methyl-2-hydroxybenzoic acid OH (II-M19) O O O

OH isophthalic acid C.OH 2-hydroxybenzoic acid (II-M12) HO O (II-M20) O OH ) therephthalic acid O (II-M13) OH O phenyl acetate (II-M21)

HN SH

r OH 4-aminobenzenethiol HO O (II-M22) benzene-1,3,5-triacetic acid (II-M14) O O -oil benzensulfonic acid OH (II-M23) HO O

O OH benzene-1,2,4-triacetic acid (II-M15) 4-(4-aminophenyl)disulfanylaniline (II-M24) HO O

O OH HO O O benzene-1,2,3-triacetic acid phenylacetamide US 2015/0279.654 A1 Oct 1, 2015 29

-continued -continued (II-M25) (II-N7) OH O O O HN ICl. NH2 acetylsalicylic acid benzene-1,2,3-triamine (II-M26) (II-O1) O OH O OH o2 No. ()- phenol derivatives, phenol (II-O2) OH o1"SoN picric acid OC OH benzene-1,2-diol (II-O3) (II-N1) HO OH

()- NH2 benzene-1,4-diol aniline derivatives, aniline (II-O4) (II-N2) NH2 HO -Cl OH NH2 benzene-1,3-diol benzene-1,2-diamine (II-O5) HO OH (II-N3)

benzene-1,4-diamine C (II-N4) benzene-1,3,5-triol (II-O6) OH HN NH benzene-1,3-diamine HO O OH (II-N5) benzene-1,2,4-triol HN NH2 (II-O7)

HO OH NH2 -ClOH benzene-1,3,5-triamine benzene-1,2,3-triol (II-N6) NH2 NH2

HN OC OH benzene-1,2,4-triamine 2-aminophenol US 2015/0279.654 A1 Oct. 1, 2015 30

-continued compound of Formula (4). Note here that the type of, and the (II-O9) process of development of aromaticity does not matter. 0049. The cyclic compounds represented by Formula (6) HO -( )– NH2 include benzofuran, benzofuranderivatives, dihydrobenzofu ran, dihydrobenzofuran derivatives, tetrahydrobenzofuran, 4-aminophenol tetrahydrobenzofuran derivatives, indole, indole derivatives, (II-O10) dihydroindole, dihydroindole derivatives, tetrahydroindole, tetrahydroindole derivatives, benzothiophene, ben Zothiophene derivatives, dihydrobenzothiophene, dihy HO1 C NH drobenzothiophene derivatives, tetrahydrobenzothiophene, 3-aminophenol tetrahydrobenzothiophene derivatives, indolizine, indolizine (II-O11) derivatives, benzimidazole, benzimidazole derivatives, inda O Zole, indazole derivatives, benzodioxole, benzodioxole derivatives, benzodithiol, benzodithiol derivatives, benzox OH azole, benzoxazole derivatives, dihydrobenzoxazole, dihy drobenzoxazole derivatives, benzothiazole, benzothiazole NH2 derivatives, dihydrobenzothiazole, dihydrobenzothiazole derivatives, benzoxathiole, benzoxathiole derivatives, dihy phenylalanine drobenzoxathiole, dihydrobenzoxathiole derivatives, benzo (II-O12) O triazole, benzotriazole derivatives, dihydrobenzotriazole, dihydrobenzotriazole derivatives, tetrahydrobenzotriazole, tetrahydrobenzotriazole derivatives, benzoxadiazole, ben OH Zoxadiazole derivatives, dihydrobenzoxadiazole, dihy NH2 drobenzoxadiazole derivatives, tetrahydrobenzoxadiazole, HO tetrahydrobenzoxadiazole derivatives, benzothiadiazole, tyrosine benzothiadiazole derivatives, dihydrobenzothiadiazole, dihydrobenzothiadiazole derivatives, tetrahydrobenzothia 0047 Referring to the cyclic compounds of Formula (6), diazole, tetrahydrobenzothiadiazole derivatives, purine, the constituting elements (elements) c1 c2, cs, ca, cs, co, c.7, purine derivatives, phthalic acid imide, phthalic acid imide cs, and co stands for at least one of carbon, nitrogen, oxygen, derivatives, phthalic anhydride, phthalic anhydride deriva Sulfur and phosphorus atoms, and these elements may pro tives, etc. There is the specific mention of 1-benzofuran, vide the respective constituting elements alone or in combi 2-benzofuran, 2,3-dihydro-1-benzofuran, 1,3-dihydro-2- nation of two or more. The constituting elements c, c and c benzofuran, 2.3.3a,7a-tetrahydro-1-benzofuran, 1.3.3a,7a as well as the constituting elements cs, c. c.7 and cs include a tetrahydro-2-benzofuran, 1H-indole, 2H-isoindole, tryp chemical bond between neighboring elements, and there is a tophan, 2,3-dihydro-1H-indole, 2,3-dihydro-1H-isoindole, chemical bond between the constituting elements c and co 2.3.3a,7a-tetrahydro-1H-indole, 2.3.3a,7a-tetrahydro-1H that may be regarded as neighboring elements. Note here that isoindole, 1-benzothiophene, 2-benzothiophene, 2,3-dihy the types of these chemical bonds do not matter. And these dro-1-benzothiophene, 1,3-dihydro-2-benzothiophene, 2.3, nine constituting elements form together a cyclic structure 3a,7a-tetrahydro-1-benzothiophene, 1.3.3a,7a-tetrahydro-2- wherein a 5-membered ring and a 6-membered ring are linked benzothiophene, indolizine, 1H-benzimidazole, together. Otherwise, the constituting elements are the same as 1H-indazole, 1,3-benzodioxol, 3H-1,2-benzodioxol, 1,3- mentioned regarding the aforesaid Formula (4) as well as a benzodithiol, 3H-1,2-benzodithiol, 1,3-benzoxazole, 1,2- a2, as a 4 and as. benzoxazole, 2.1-benzoxazole, 2,3-dihydro-1,3-benzox 0048. The cyclic compound of Formula (6), too, shows azole, 2,3-dihydro-1,2-benzoxazole, 1,3-dihydro-2.1- aromaticity under conditions under which it is used, as is the benzoxazole, 1,3-benzothiazole, 1,2-benzothiazole, 2.1- case with the aforesaid compound of Formula (4). The con benzothiazole, 2,3-dihydro-1,3-benzothiazole, 2,3-dihydro ditions under which this compound shows aromaticity would 1,2-benzothiazole, 1,3-dihydro-2,1-benzothiazole, 1,3- appear to include, in addition to the aromaticity that this benzoxathiol, 3H-2,1-benzoxathiol, 3H-1,2-benzoxathiol, compound has in itself ionization or radicalization of the 3a,7a-dihydro-1,3-benzoxathiol, 3a,7a-dihydro-3H-2, 1-ben elements (atoms) c1 c2, cs, ca, cs, co, c.7, cs, and co, changes Zoxathiol, 3a,7a-dihydro-3H-1,2-benzoxathiol, 1H-benzot in the types of bonds of the elements c, ca, cs, ca, c. c. c.7. riazole, 1-hydroxybenzotriazole, 3a,7a-dihydro-1H-benzot cs, and co, detachment of atoms or functional groups attached riazole, 2.3.3a,7a-tetrahydro-1H-benzotriazole, 2,13 to the elements c. c2, ca, ca, c. co, c.7, cs, and co, changes in benzoxadiazole, 1,2,3-benzoxadiazole, 1,3-dihydro-2,1,3- the types of bonds of atoms or functional groups attached to benzoxadiazole, 3a,7a-dihydro-1,2,3-benzoxadiazole, 1.3, the elements c1 c2, cs, ca, cs, co, c.7, cs, and co, ionization or 3a,7a-tetrahydro-2,1,3-benzoxadiazole, 2,3,3a,7a radicalization of atoms attached to the elements c, c. c. ca. tetrahydro-1,2,3-benzoxadiazole, 2,1,3-benzothiadiazole, c. c. c.7, cs, and co, ionization or radicalization of functional 1,2,3-benzothiadiazole, 1,3-dihydro-2,1,3-benzothiadiazole, groups attached to the elements c. c2cs, ca, c. c. c.7, cs and 3a,7a-dihydro-1,2,3-benzothiadiazole, 1.3.3a,7a-tetrahydro co, chemical changes such as oxidization or reduction of 2,1,3-benzothiadiazole, 2.3.3a,7a-tetrahydro-1,2,3-ben functional groups attached to the elements c. c2, cs, ca, c. ca. Zothiadiazole, 9H-purine, adenine, guanine, hypoxanthine, c.7, cs, and co, application of extraneous light, electromagnetic Xanthine, theobromine, caffeine, uric acid, isoguanine, waves, and Voltages, etc. as is the case with the aforesaid phthalic acid imide, phthalic anhydride, etc. US 2015/0279.654 A1 Oct. 1, 2015 31

0050. By way of example but not by way of limitation, -continued typical specific structures of the above-exemplified cyclic compounds represented by Formula (6) are given below. (III-B2a)

(III-A1a) O) O 2,3-dihydro-1H-indole (III-B2b)

1-benzofuran NH (III-A1b) CO 2,3-dihydro-1H-isoindole O (III-B3a) 2-benzofuran (III-A2a) O) 2,3,3a.7a-tetrahydro-1H-indole OC) (III-C1a) 2,3-dihydro-1-benzofuran N (III-A2b) S 1-benzothiophene CO (III-C1b) 1,3-dihydro-2-benzofuran (III-A3a) N1S/21 N2\ 2-benzothiophene CC) (III-C2a) 2,3,3a,7a-tetrahydro-1-benzofuran (III-A3b) CO) 2,3-dihydro-1-benzothiophene CO (III-C2b) 1,3,3a,7a-tetrahydro-2-benzofuran (III-B1a) O 2,3-dihydro-1-benzothiophene / (III-C3a)

1H-indole (III-B1b) O) 2,3,3a,7a-tetrahydro-1-benzothiophene O (III-C3b) 2H-isoindole (III-B1c) O 1,3,3a,7a-tetrahydro-2-benzothiophene (III-D) 21 e (SJ N-N/ tryptophan indolizine

US 2015/0279.654 A1 Oct. 1, 2015 34

-continued -continued (III-O7) (III-N3b) OH S N NH M N21 N N H ls Y-OH 2,3,3a,7a-tetrahydro-1,2,3-benzothiadiazole HO N N (III-O) Uric acid (III-O8) O) NH2 9H-Purine N 21 y (III-O1) ls NH HO N N Soguanine N (III-P1) Na y O ls N N H Adenine NH (III-O2) OH O

N phthalimide (III-P2) Na y O ls N N H Guanine (III-O3) OH O Na Ny phthalic anhydride N lsN H 0051 Referring to the cyclic compounds of formula (7), Hypoxanthine the constituting elements (atoms) d, d, d, d, ds, do d7, and (III-O4) ds stands for at least one of carbon, nitrogen, oxygen, Sulfur =N and phosphorus atoms, and usually these elements provide the respective constituting elements, although they may be N \ / NH used in combination of two or more. The constituting ele 2 ments d.d. d, d, ds, d, d7, and ds include a chemical bond HO N between neighboring constituting elements, and there are chemical bonds between three neighboring constituting ele Xanthine ments provided that the constituting elements d and d, are (III-O5) regarded as neighboring elements. Note here that the types of OH these chemical bonds do not matter. These eight constituting elements form together a cyclic structure in a form in which a 5-membered ring is linked to a 5-membered ring. Otherwise, the same as applied to the aforesaid formula (4) anda, a2, as a and as will hold true. 0.052 The cyclic compound of formula (6), too, takes on Theobromine aromaticity under conditions under which it is used, as is the (III-O6) case with the aforesaid compounds of formula (4). The con HO ditions for this compound to take on aromaticity would appear to include, in addition to the fact that this compound possesses aromaticity in itself, ionization or radicalization of V / NH the elements (atoms) d, d2, d, dads, d, d7, and ds, changes 2 in the types of bonds of the elements d.d. d, d, ds, de d7. HO N and ds, detachment of atoms or functional groups attached to the elements at the 1 to 8 positions, changes in the types of Caffeine bonds of atoms or functional groups attached to the elements d, d2, d, d, ds, d, d7, and ds, ionization or radicalization of

US 2015/0279.654 A1 Oct. 1, 2015 36

4H-thieno 3.2-bipyrrole, 6-fluoro-5-methyl-4H-furo3.2-b nitride oxides (SiNO, where x>y>0). It is to be noted that pyrrole, 6H-cyclopentacfuran, 6H-cyclopentacthiophene, these compounds may depart more or less from their stoichio 6H-furo3.2-bifuran-5-one, 6H-furo3.2-bipyrrole, metric compositions. 6H-thieno3.2-bipyrrole, 6H-thieno 3,4-cpyrrole, 6-me 0059. The material that is dipped together with such a thyl-1,4-dihydropyrrolo3.2-bipyrrole, 6-methyl-1H-furo2. nitrogen-containing silicon compound in the treating Solution 3-dimidazole, 6-methyl-4H-thieno3.2-bipyrrole, 6-methyl for etching or cleaning is preferably an oxygen-containing furo32-bifuran, 6-methylthieno 3.2-bfuran, silicon compound or a carbon-containing silicon compound. 6-methylthieno 3.2-bithiophene, 6-propan-2-yl-4H-thieno The oxygen-containing silicon compound or carbon-contain 3.2-bipyrrole, furo3.2-bfuran, furo3,2-bfuran-5-ol, furo ing silicon compound includes silicon oxides (SiO), silicon 3.2-bipyrrole-3,4-diamine, furo3,4-d1.2 oxazole, N.N- carbides (SiCN), SiOF (also called FSG), SiOC, SiOH, and diethyl-2-(4H-furo3.2-bipyrrol-2-yl)ethylamine, N,N- TEOS (tetraethoxysilane), or PSG (phosphorus silicon dimethyl-1-(4H-thieno 32-bipyrrol-6-yl)methylamine, glass), BPSG (boron phosphor silicate glass) and SOG (spin N,N-dimethyl-2-(4H-thieno 32-bipyrrol-6-yl)ethylamine, on glass: SiO2) that contain, or are combined with, these N-ethyl-1H-pyrrolo3.2-bipyrrole-4-amine, N-methyl-1H materials, or a material that is used as a semiconductor struc thieno2,3-dimidazole-2-amine, thieno 32-bifuran, thieno ture called Low-k or an insulating material. It is to be noted 3.2-bfuran-4-oxide, thieno3.2-bithiophene, thieno 3.2-b that these compounds may depart more or less from their thiophe-4-oxide, thieno3.2-bithiophene-2,5-dithiol, thieno Stoichiometric compositions too. 3,2-d1.2thiazole, thieno3,4-bfuran, thieno 3,4-d1.2 thiazole, trimethyl(4H-thieno 3.2-bipyrrol-6-yl methyl) 0060 According to the invention, the etching of silicon aZanium, etc. nitrides may be inhibited or reduced, and etch selectivity is 0054 Although the amount of the aforesaid cyclic com defined as an index to the etch rate of the silicon nitride pound(s) to be added differs depending on the types of the compound with respect to the silicon oxide. Specifically, an coexisting compounds represented by Formulae (1), (2) and etch rate ratio between thermally oxidized silicon and CVD (3) and their own type(s), the cyclic compound(s) may be silicon nitride in an aqueous solution of hydrofluoric acid contained in an amount of 0.001 mass % or greater per the (CVD-silicon nitride etch rate/thermally oxidized siliconetch total amount of the solution to be added. Although there is no rate) is defined as etch selectivity. This etch selectivity is less particular upper limit, it is preferably about 2 mass %. than 1, preferably not greater than 0.8, and more preferably 0055. The treating solution may further contain a buffer not greater than 0.5 when a solution containing the constitut comprising a weak acid and any desired alkali species for the ing element(s) of the invention Such as the aforesaid Surfac purpose of proper pH value regulation and keeping its pH tant is compared with a reference sample consisting of value constant. Although the content of such a buffer may be hydrofluoric acid alone. controlled to the desired amount needed for pH regulation, it 0061 The treating solution containing the additive(s) of should preferably be regulated in Such a way as to have no the invention is preferably applied to a treating step of a adverse influence on the actions of both the aforesaid main process for producing a large scale integration circuit formed ingredient or Surfactant and inhibitor. ona Siwafer or Sithin film structure or a liquid crystal display 0056 Although there is no particular limitation on the thin-film transistor formed on a glass Substrate, in which weak acid forming a part of the buffer, there is the mention of treating step the aforesaid oxygen- or carbon-containing sili for instance, phosphoric acids such as phosphoric acid, con con compound(s) and nitrogen-containing silicon compound densed phosphoric acid, poly-phosphoric acid and metaphos (s) exist while exposed to view. In particular, the treating phoric acid, carboxyl group-containing organic acids such as solution of the invention lends itself to steps of etching or citric acid, malonic acid and malic acid, and amino acids. For cleaning the oxygen- or carbon-containing silicon compound the alkali species, use may be made of ammonia and amines. (s) that exists in a form of an insulation structure, a passivation Note here that the type of alkali species does not matter. structure or etching residues using hydrofluoric acid. 0057 The treating solution may further contain an organic 0062. The treating solution of the invention may be used Solvent. The organic solvent is added for the purpose of regu with any of a spray type single wafer processing apparatus, a lating its relative permittivity and enhancing its treatment dip type bath apparatus, and a spray type batch apparatus with performance. For Such an organic solvent, by way of example no difficulty. To prevent oxidation of the surface of a device, but not by way of limitation, any desired organic solvent may the treatment may be carried out in an atmosphere using a be selected from known materials miscible with water, for nitrogen gas or other inert gas. instance, isopropyl alcohol, N-methylpyrrolidone, dimethyl Sulfoxide, dimethylformamide, methanol, ethanol, butanol, 0063 Although there are variations in the conditions propanol, and ethylene glycol. The content of the organic involved depending on the type of the insulating film used, the solvent is usually 0.1 to 90 mass %, and preferably less than treatment may generally be carried out at 20 to 70° C. for 30 mass % per the treating solution. about 0.5 to 40 minutes. However, it is to be noted that there 0.058 Herein, the aforesaid surfactant or the additive com are changes in the optimum conditions depending on the prising a combination of that Surfactant and the aforesaid etching conditions for what is etched, the concentration of the cyclic compound(s) is often called the inhibitor. The additive additive(s), etc.; the best conditions may be determined as (inhibitor) of the invention may be added to such a treating necessary. Solution as described above to selectively protect nitrogen 0064. It is possible to rinse what has been treated with the containing silicon compounds from etching or corrosion. The treating Solution by direct use of water, and it is possible to nitrogen-containing silicon compound used herein is a gen carry out dipping treatment for a long period of time as well. eral name for compounds containing nitrogen and silicon Note here that the “water used herein includes pure water, optionally with other element(s) such as silicon nitrides ultrapure water, etc., which may be selectively used as nec (SiN.), silicon oxynitrides (SiO, N, where x>y>0) and silicon essary. US 2015/0279.654 A1 Oct. 1, 2015 37

EXAMPLES treating Solutions indicated as Samples 21-26. There was also 0065. Some specific embodiments of the invention are comparative Sample 20 for reference prepared to which any now explained with reference to the following examples. cyclic compound was not added. 0070. Such test pieces as used in Example 1 were dipped in Example 1 the obtained treating solutions to measure the etch rates of the respective films. As in Example 1, the etch rate ratios and etch Addition of the Anionic Surfactant selectivity were found from the respective etch rates. The 0066 Sample 1: (1)-1 isopropylnaphthalenesulfonic acid, results are tabulated in Table 2. Sample 2: (1)-2 diisopropyl naphthalenesulfonic acid, and Sample 3: (1)-4 dibutyl naphthalenesulfonic acid, all as the TABLE 2 compounds represented by Formula (1), and Sample 4: (2)-1 Sample No. Heterocyclic Compound pH SiN Etch-rate (nm/min) a naphthalenesulfonic acid/formalin condensate as the com 2O not used 3 O.S pound represented by Formula (2) were added in an amount 21 A. 3 O.2 of 0.05 mass % to an aqueous solution of hydrofluoric acid 22 B 3 O.3 having a concentration of 1 mass % to prepare treating solu 23 C 3 O.2 tions. A surfactant-free aqueous solution consisting of 24 D 3 O.1 hydrofluoric acid alone was also prepared as comparative 25 E 3 O.2 Sample 0. 26 F 3 O.2 0067. A 1,000-nm thick, thermally oxidized silicon (Th— Sample No. SiO, Etch-rate (nm/min) Etch-rate ratio Etch Selectivity SiO2) was formed on an 8-inch size silicon wafer, and a 2O S.6 O.09 600-nm thick silicon nitride (SiN) film was formed by a CVD 21 S.6 0.4 O.04 process to obtain a test piece. Note here that the conditions for 22 S.6 O6 O.OS forming the respective films are not explained anymore 23 5.8 0.4 O.O3 because they have generally been known in the art. The 24 S.6 O.2 O.O2 obtained test piece was dipped in the treating solution pre 25 S.6 0.4 O.04 pared as described above to measure the etch rates of the 26 S.6 0.4 O.04 respective films. At this time the treating temperature and A: imidazole B: histidine time were 25°C. and 10 minutes to 30 minutes, respectively. C: phenylalanine The etch rate ratio was found as the ratio to the etch rate of the D: benzimidazole Surfactant-free comparative sample, and etch selectivity was E: benzotriazole found as the etch rate of silicon nitride/etch rate of thermally F: tryptophan oxidized silicon. The results are tabulated in Table 1. (0071. From the results of Table 2, it has been found that TABLE 1. good results are obtained with all the samples as compared with Example 1, and that Samples 23 and 24 in particular are Sample No. Surfactant pH SiN Etch-rate (nm/min) superior to the rest. O not used 3 O.6 1 (1)-1 3 O.S Example 3 2 (1)-3 3 O.S 3 (1)-4 3 0.4 4 (2)-1 3 O.S Estimation of the Concentration of Cyclic Sample No. SiO2 Etch-rate (nm?min) Etch-rate ratio Etch Selectivity Compounds O S.6 O.11 0072 Example 2 was repeated with the exception that 1 S.6 O.83 O.09 Sample 24: benzimidazole of the cyclic compounds was 2 S.6 O.83 O.09 3 S.6 O.67 O.O7 added in amounts of 0.001 mass % (Sample 31), 0.005 mass 4 S.6 O.83 O.09 % (Sample 32), 0.01 mass % (Sample 33), 0.05 mass % (Sample 34) and 0.1 mass % (Sample 35) to prepare treating solutions as Samples 31-35. There was comparative Sample 0068. From the results of Table 1, it has been found that all 30 for reference provided to which no cyclic compound was the samples having the additive added to them make Sure a added. constant anticorrosion effect on the silicon nitride, and that sample (1)-4 in particular has an improved anticorrosion 0073. Such test pieces as used in Example 1 were dipped in effect. the obtained treating solutions to measure the etch rates of the respective films. As in Example 1, the etch rate ratios and etch Example 2 selectivity were found from the respective etch rates. The results are tabulated in Table 3. Estimation of the Cyclic Compound Species TABLE 3 0069. As in Example 1 there was an aqueous solution of hydrofluoric acid provided at a concentration of 1 mass %. Sample No. Cyclic Compound (%) pH SiN Etch-rate (nm/min) (1)-1: Isopropyl naphthalenesulfonic acid was added in an 30 O 3 O.S amount of 0.05 mass % to the aqueous solution. Further, such 31 O.OO1 3 0.4 cyclic compounds as shown in Table 2 were added in an 32 O.OOS 3 O.2 amount of 0.1 mass % to that aqueous solution to prepare US 2015/0279.654 A1 Oct. 1, 2015 38

TABLE 3-continued amount of 0.005 mass %, and that effect becomes noticeable in an amount of 0.02 mass % or greater. 33 O.O1 3 O.1 34 O.OS 3 O.1 35 O.1 3 O.1 Example 5 Sample No. SiO, Etch-rate (nm/min) Etch-rate ratio Etch Selectivity Estimation I of the Concentration of Hydrofluoric 30 S.6 O.09 Acid 31 S.6 O.8 O.O7 32 S.6 0.4 O.04 33 S.6 O.2 O.O2 0078 Provision was made of aqueous solutions having 34 S.6 O.2 O.O2 varying concentrations of hydrofluoric acid: Sample 51 (0.1 35 S.6 O.2 O.O2 mass %), Sample 52 (0.5 mass %), Sample 53 (2 mass %), Heterocylic compound; benzimidazole Sample 54 (5 mass %), Sample 55 (10 mass %) and Sample 56 (15 mass %). Using these samples with and without the 0074. From the results of Table 3, it has been found that inhibitor added to them, the etch rate of silicon nitride films even Sample 31 (0.001 mass %) works, but Sample 32 (0.005 was measured: the etch rate ratios were determined in the mass %) works better, with a leveling off in Samples 33-35 presence and absence of the inhibitor. Sample 1: (1)-1 iso (more than 0.01 mass %). propylnaphthalenesulfonic acid represented by Formula (1) as the inhibitor and benzimidazole as the cyclic compound Example 4 were added in the respective amounts of 0.05 mass % and 0.01 mass %. Provision was also made of silicon nitride film test Estimation of the Concentration of Surfactant pieces similar to those in Example 1. Treating conditions, etc. were pursuant to Example 1 too. The results are tabulated in 0075 Benzimidazole was added in an amount of 0.01 Table 5. mass % to the aqueous solution of hydrofluoric acid having a concentration of 1 mass %, and compound (1)-1 represented TABLE 5 by Formula (1): isopropyl-naphthalenesulfonic acid was Hydrofluoric Inhibitor Inhibitor added to the obtained solution in amounts of 0.001 mass % Sample No. acid (%) (used nm min) (not used nimmin) (Sample 41), 0.005 mass % (Sample 42), 0.01 mass % (Sample 43), 0.02 mass % (Sample 44), 0.03 mass % (Sample 51 O.1 O.OS O.2 52 O.S O.1 0.4 45), 0.05 mass % (Sample 46) and 0.1 mass % (Sample 47) as 53 2 O.2 1.3 shown in Table 4 to prepare treating Solutions as Samples S4 5 O.9 2.9 41-47. There was comparative Sample 40 for reference pro 55 10 2.7 5.4 vided to which no surfactant was added. 56 15 6.5 8.7 0076 Such test pieces as used in Example 1 were dipped in Sample No. Etch-Rate Ratio the obtained solutions to measure the etch rates of the respec tive films. As in Example 1, the etch rate ratios and etch 51 O.3 selectivity were found from the respective etch rates. The 52 O.3 results are tabulated in Table 4. 53 O.2 55 O.S TABLE 4 56 0.7 Sample No. Surfactant (%) SiN Etch-rate (nm?min)

40 O O6 007.9 From the results of Table 5, it has been found that 41 O.OO1 O6 Sample 53 having a hydrofluoric acid concentration of 2 mass 42 O.OOS O.S % shows the lowest etch rate ratio: satisfactory results are 43 O.O1 O.S obtained. 44 O.O2 0.4 45 O.O3 O.2 46 O.OS O.1 Example 6 47 O.1 O.1 Surfactant: (1)-1 Estimation II of the Concentration of Hydrofluoric SiO, Etch-rate Etch-rate Etch Acid Sample No. (nmmin) ratio selectivity 0080. As in Example 5, aqueous solutions of hydrofluoric 40 S.6 O.11 acid having varying concentrations were provided as Sample 41 S.6 1 O.11 42 S.6 O.8 O.09 61 to Sample 66. In each sample with and without the inhibi 43 S.6 O.8 O.09 tor added to it, the etch rates of a silicon nitride film and a 44 S.6 0.7 O.O7 silicon oxide film were measured to find etch selectivity in the 45 S.6 O.3 O.04 presence and absence of the inhibitor. The inhibitor used was 46 S.6 O.2 O.O2 similar to that used in Example 5, and the silicon nitride 47 S.6 O.2 O.O2 film/silicon oxide film test pieces used were equivalent to those used in Example 1. The treating conditions, etc. were 0077. From the results of Table 3, it has been found that the pursuant to Example 1 too. The results are tabulated in Table Surfactant starts to develop its anticorrosion effect in an 6. US 2015/0279.654 A1 Oct. 1, 2015 39

TABLE 6 Example 8 Sample Hydrofluoric SiN Etch-rate No. acid (%) Inhibitor (nmmin) Estimation II of pH 61 O.1 (not used) O.2 (used) O.OS I0084 As in Example 7, the pH values were regulated to 62 O.S (not used) 0.4 provide Sample 81 to Sample 85 having pH values of 2 to 6 as (used) O.1 shown in Table 8. In each sample with and without the inhibi 63 2 (not used) 1.3 (used) O.2 tor added to it, the etch rates of a silicon nitride film and a 64 5 (not used) 2.9 silicon oxide film were measured to find etch selectivity in the (used) O.9 presence and absence of the inhibitor. The inhibitor used was 65 10 (not used) 5.4 (used) 2.7 similar to that used in Example 5, and the silicon nitride 66 15 (not used) 8.7 film/silicon oxide film test pieces were equivalent to those (used) 6.5 used in Example 1. The treating conditions, etc. were pursu Sample No. SiO, Etch-Rate (nm/min) Etch Selectivity ant to Example 1 too. The results are tabulated in Table 8.

61 O.2 1 TABLE 8 O.2 O.25 62 2.6 O.15 Sample SiNEtch- SiO, Etch 2.6 O.04 No. pH Inhibitor rate (nmmin) rate (nmmin) 63 11.9 O.11 11.9 O.O2 81 2 (not used) O.8 7.1 64 3O.S O.10 (used) O.2 7.1 3O.S O.O3 82 3 (not used) 0.7 9.8 65 67.0 O.08 (used) 0.4 8.9 67.0 O.04 83 4 (not used) O.S 9.8 66 114.5 O.08 (used) 0.4 8.9 114.5 O.O6 84 5 (not used) 0.4 7.3 (used) O.3 6.9 0081 From the results of Table 6, it has been found that 85 6 (not used) O.O7 O.2 Sample 63 having a hydrofluoric acid concentration of 2 mass (used) O.O6 O.2 % shows the lowest etch electivity: satisfactory results are Sample No. Etch Selectivity obtained. 81 O.11 Example 7 O.O3 82 O.O7 O.04 Estimation I of pH 83 O.OS O.04 0082. The pH value of an aqueous solution containing 10 84 O.OS mass % of ammonium phosphate and 1 mass % of hydrof O.04 luoric acid was regulated to provide Sample 71 to Sample 75 85 O3S having pH values of2 to 6, as shown in Table 7. The pH values O.3 were regulated by use of ammonia water. In each sample with and without the inhibitor added to it, the etch rates of a silicon nitride film and a silicon oxide film were measured to find an 0085. From the results of Table 8, it has been found that etch rate ratio in the presence and absence of the inhibitor. The Sample 81 of pH2 shows the lowest etch selectivity upon inhibitor used was similar to that used in Example 5, and the addition of the inhibitor, and the etch selectivity grows high silicon nitride film/silicon oxide film test pieces used were with an increasing pH value. equivalent to those used in Example 1, and consisted only of the silicon nitride film. The treating conditions, etc. were pursuant to Example 1 too. The results are tabulated in Table Example 9 7. Estimation I of the Buffer TABLE 7 I0086 A buffer comprising 10 mass % of a weak acid and Sample Inhibitor Inhibitor Etch-rate analkali species and an aqueous solution containing 1 mass 96 No. pH (used nm min) (not used nimmin) ratio of hydrofluoric acid were prepared to provide Sample 91 to 71 2 O.2 O.8 O.3 72 3 0.4 0.7 O.6 Sample 94 as shown in Table 9. In each sample with and 73 4 0.4 O.S O.8 without the inhibitor added to it, the etch rate of a silicon 74 5 O.3 0.4 O.8 nitride film was measured to find an etch rate ratio in the 75 6 O.O6 O.O7 O.8 presence and absence of the inhibitor. The inhibitor used was similar to that used in Example 5, and the silicon nitride film 0083. From the results of Table 7, it has been found that test pieces used were equivalent to those used in Example 1, Sample 71 having a pH value of 2 shows the lowest etch rate and consisted only of the silicon nitride film. The treating ratio, and as the pH value grows large, it causes the etch rate conditions, etc. were pursuant to Example 1 too. The results ratio to grow high, with no change at pH values of 4 or greater. are tabulated in Table 9. US 2015/0279.654 A1 Oct. 1, 2015 40

TABLE 9 hydrofluoric acid in Sucha way as to have Such concentrations of 0 to 50 mass % as shown in Table 11, thereby preparing Sample Inhibitor Inhibitor Etch-rate such Sample 110 to Sample 115 as shown in Table 11. In each No. Buffer (used nimmin) (not used nimmin) ratio sample with and without the inhibitor added to it, the etch rate 91 AP 0.4 O.6 0.7 of a silicon nitride film was measured to find an etch rate ratio 92 AC 0.4 O.6 0.7 in the presence and absence of the inhibitor. The inhibitor 93 MA 0.4 0.7 O6 used was similar to that used in Example 5, and the silicon 94 MA O.3 0.7 0.4 nitride film test pieces used were equivalent to those used in AP: ammonium phosphate Example 1, and consisted only of the silicon nitride film. The AC: ammonium citrate treating conditions, etc. were pursuant to Example 1 too. The MA: malonic acid ammonium results are tabulated in Table 11. MA: malic acid ammonium 0087. From the results of Table 9, it has been found that TABLE 11 Sample 94 having malic acid ammonium added to it shows the lowest etch rate ratio, and the etch rate ratio increases in Sample DMSO Inhibitor Inhibitor Etch-rate order of Sample 93 and Samples 91 and 92. No. (%) (used nm min) (not used nm min) ratio 110 O O.1 O6 O.2 Example 10 111 5 O.3 O6 O.S 112 10 0.4 O.S O.8 Estimation II of the Buffer 113 2O 0.4 O.S O.8 0088 As in Example 9, the respective buffers were used to 114 30 0.4 0.4 1 provide Sample 101 to Sample 104 as shown in Table 10. In 115 50 O.2 O.2 1 each sample with and without the inhibitor added to it, the etch rates of a silicon nitride film and a siliconoxide film were 0091. From the results of Table 11, it has been found that measured to find etch selectivity in the presence and absence Sample 110 having no organic solvent (0%) added to it shows of the inhibitor. The inhibitor used was similar to that used in the lowest etch rate ratio, and the etch rate ratio grows high in Example 5, and the silicon nitride film/silicon oxide film test proportion to the content of the organic solvent, while the etch pieces were equivalent to those used in Example 1. The treat ing conditions, etc. were pursuant to Example 1 too. The ratio of Sample 114 of 30% in concentration reaches 1. results are tabulated in Table 10. Example 12 TABLE 10 Estimation II of the Organic Solvent DMSO Sample SiNEtch- SiO2 Etch No. Buffer Inhibitor rate (nmmin) rate (nmmin) 0092. As in Example 11, such Samples 120 to 125 as 101 AP (not used) O6 9.9 shown in Table 12 were prepared. In each sample with and (used) 0.4 8.9 without the inhibitor added to it, the etch rates of a silicon 102 AC (not used) O6 8.3 nitride film and a silicon oxide film were measured to find (used) 0.4 8.5 103 MA (not used) 0.7 8.8 etch selectivity in the presence and absence of the inhibitor. (used) 0.4 9.O The inhibitor used was similar to that used in Example 5, and 104 MA (not used) 0.7 8.3 the silicon nitride film/silicon oxide film test pieces used were (used) O.3 8.5 equivalent to those used in Example 1. The treating condi Sample No. Etch Selectivity tions, etc. were pursuant to Example 1 too. The results are tabulated in Table 12. 101 O6 O.04 TABLE 12 102 O.O7 O.O6 Sample DMSO SiNEtch- SiO2 Etch 103 O.08 No. (%) Inhibitor rate (nmmin) rate (nmmin) O.04 104 O.08 120 O (not used) O6 S.6 O.04 (used) O.1 S.6 121 5 (not used) O6 4.5 AP: ammonium phosphate (used) O.3 4.5 AC: ammonium citrate 122 10 (not used) O.S 3.7 MA: malonic acid ammonium (used) 0.4 3.7 MA: malic acid ammonium 123 2O (not used) O.S 2.4 (used) 0.4 2.4 0089. From the results of Table 10, it has been found that 124 30 (not used) 0.4 1.5 Sample 101 having ammonium phosphate added to it, Sample (used) 0.4 1.5 103 having malonic acid ammonium added to it, and Sample 125 50 (not used) O.2 0.4 104 having malic acid ammonium added to it shows the (used) O.2 0.4 lowest etch rate ratio upon addition of the inhibitor. Sample No. Etch Selectivity

Example 11 120 O.11

Estimation I of the Organic Solvent DMSO 121 O.13 0090. An organic solvent: dimethyl sulfoxide (DMSO) was added to an aqueous solution containing 1 mass % of US 2015/0279.654 A1 Oct. 1, 2015 41

TABLE 12-continued equivalent to those used in Example 1. The treating condi tions, etc. were pursuant to Example 1 too. The results are 122 O.14 tabulated in Table 14. O.11 123 O.21 O.17 TABLE 1.4 124 0.27 0.27 Sample NMP SiN Etch- SiO, Etch 125 OSO No. (%) Inhibitor rate (nmmin) rate (nmmin) OSO 140 O (not used) O.6 S.6 (used) O.1 S.6 0093. From the results of Table 12, it has been found that 141 5 (not used) O.6 4.4 (used) O.3 4.4 Sample 120 having no organic solvent (0%) added to it shows 142 10 (not used) O.S 3.5 the lowest etch selectivity upon addition of the inhibitor, the (used) O.3 3.5 etch selectivity grows high in proportion to the content of the 143 2O (not used) 0.4 2.3 organic solvent, and the etch selectivity of Sample 124 having (used) O.3 2.3 144 30 (not used) O.3 1.4 an organic solvent content of 30% is the same regardless of (used) O.3 1.4 the presence or absence of the inhibitor. It has also been found 145 50 (not used) O.2 O.3 that both the etch rates of Sample 125 having an organic (used) O.2 O.3 solvent content of 50% get even lower. Sample No. Etch Selectivity

Example 13 140 O.11 Estimation I of the Organic Solvent NMP 141 O.14 142 O.14 0094 Zero to 50 mass % of an organic solvent: N-meth O.09 ylpyrrolidone (NMP) were mixed with an aqueous solution of 143 O.17 1 mass % of hydrofluoric acid in Such a way as to have Such O.13 concentrations as shown in Table 13 thereby preparing Such 144 O.21 O.21 Samples 130 to 135 as shown in Table 13. In each sample with 145 O.67 and without the inhibitor added to it, the etch rate of a silicon O.67 nitride film was measured to find an etch rate ratio in the presence and absence of the inhibitor. The inhibitor used was similar to that used in Example 5, and the silicon nitride film 0097. From the results of Table 14, it has been found that test pieces used were equivalent to those used in Example 1, Sample 140 having no organic solvent (0%) added to it shows and consisted only of the silicon nitride film. The treating the lowest etch selectivity upon addition of the inhibitor, the conditions, etc. were pursuant to Example 1 too. The results etch selectivity grows high in proportion to the content of the are tabulated in Table 13. organic solvent, and the etch selectivity of Sample 144 having an organic solvent content of 30% is the same regardless of TABLE 13 the presence or absence of the inhibitor. It has also been found that both the etch rates of Sample 145 having an organic Sample NMP Inhibitor Inhibitor Etch-rate solvent content of 50% get even lower. No. (%) (used nm min) (not used nimmin) ratio 130 O O.1 O.6 O.17 Example 15 131 5 O.3 O.6 OSO 132 10 O.3 O.S O.6O Estimation I of the Organic Solvent Ethylene Glycol 133 2O O.3 0.4 0.75 134 30 O.3 O.3 1.O 0.098 Zero to 50 mass % of an organic solvent ethylene 135 50 O.2 O.2 1.O glycol (EG) were mixed with an aqueous Solution containing 1 mass % of hydrofluoric acid in Such a way as to have Such 0095. From the results of Table 13, it has been found that concentrations as shown in Table 15 thereby preparing Such Sample 130 having no organic solvent (0%) added to it shows Samples 150 to 155 as shown in Table 15. In each sample with the lowest etch rate ratio, and the etch rate ratio grows high in and without the inhibitor added to it, the etch rate of a silicon proportion to the content of the organic solvent, while the etch nitride film was measured to find an etch rate ratio in the ratio of Sample 134 of 30% in concentration reaches 1. presence and absence of the inhibitor. The inhibitor used was similar to that used in Example 5, and the silicon nitride film Example 14 test pieces used were equivalent to those used in Example 1, and consisted only of the silicon nitride film. The treating Estimation II of the Organic Solvent NMP conditions, etc. were pursuant to Example 1 too. The results are tabulated in Table 15. 0096. As in Example 13, such Samples 140 to 145 as TABLE 1.5 shown in Table 14 were prepared. In each sample with and without the inhibitor added to it, the etch rates of a silicon Sample EG Inhibitor Inhibitor Etch-rate nitride film and a silicon oxide film were measured to find No. (%) (used nm min) (not used nimmin) ratio etch selectivity in the presence and absence of the inhibitor. 150 O O.1 O6 O.17 The inhibitor used was similar to that used in Example 5, and 151 5 O.2 0.7 O.29 the silicon nitride film/silicon oxide film test pieces used were US 2015/0279.654 A1 Oct. 1, 2015 42

TABLE 15-continued Example 17 Sample EG Inhibitor Inhibitor Etch-rate Estimation I of the Organic Solvent IPA No. (%) (used nm min) (not used nimmin) ratio 152 10 O.3 0.7 O43 0102 Zero to 50 mass % of an organic solvent isopropyl 153 2O O.S 0.7 O.71 alcohol (IPA) were mixed with an aqueous Solution contain 154 30 O.S 0.7 O.71 ing 1 mass % of hydrofluoric acid in Such a way as to have 155 50 O.S O.S 1.O Such concentrations as shown in Table 17 thereby preparing such Samples 170 to 175 as shown in Table 17. In each sample with and without the inhibitor added to it, the etch rate of a 0099 From the results of Table 15, it has been found that silicon nitride film was measured to find an etch rate ratio in Sample 150 having no organic solvent (0%) added to it shows the presence and absence of the inhibitor. The inhibitor used the lowest etch rate ratio, and the etch rate ratio grows high in was similar to that used in Example 5, and the silicon nitride proportion to the content of the organic solvent, while the etch film test pieces used were equivalent to those used in Example ratio of Sample 155 of 50% in concentration reaches 1. 1, and consisted only of the silicon nitride film. The treating conditions, etc. were pursuant to Example 1 too. The results Example 16 are tabulated in Table 17.

Estimation II of the Organic Solvent Ethylene Glycol TABLE 17 0100. As in Example 15, such Samples 160 to 165 as Sample IPA Inhibitor Inhibitor Etch-rate shown in Table 16 were prepared. In each sample with and No. (%) (used nm min) (not used nimmin) ratio without the inhibitor added to it, the etch rates of a silicon 170 O O.1 O6 O.17 nitride film and a silicon oxide film were measured to find 171 5 O.3 0.7 O43 etch selectivity in the presence and absence of the inhibitor. 172 10 O.3 O6 O.S The inhibitor used was similar to that used in Example 5, and 173 2O O.S O.S 1.O the silicon nitride film/silicon oxide film test pieces used were 174 30 0.4 0.4 1.O equivalent to those used in Example 1. The treating condi 175 50 O.3 O.3 1.O tions, etc. were pursuant to Example 1 too. The results are tabulated in Table 16. (0103. From the results of Table 17, it has been found that Sample 170 having no organic solvent (0%) added to it shows TABLE 16 the lowest etch rate ratio, and the etch rate ratio grows high in proportion to the content of the organic solvent, while the etch Sample EG SiNEtch- SiO2 Etch No. (%) Inhibitor rate (nmmin) rate (nmmin) ratio of Sample 173 of 20% in concentration already reaches 1. 160 O (not used) O.6 S.6 (used) O.1 S.6 Example 18 161 5 (not used) 0.7 5.3 (used) O.2 5.3 162 10 (not used) 0.7 4.8 Estimation II of the Organic Solvent IPA (used) O.3 4.8 163 2O (not used) 0.7 4.1 0104. As in Example 17, such Samples 180 to 185 as (used) O.S 4.1 shown in Table 18 were prepared. In each sample with and 164 30 (not used) 0.7 3.3 (used) O.S 3.3 without the inhibitor added to it, the etch rates of a silicon 16S 50 (not used) O.S 1.8 nitride film and a silicon oxide film were measured to find (used) O.S 1.8 etch selectivity in the presence and absence of the inhibitor. The inhibitor used was similar to that used in Example 5, and Sample No. Etch Selectivity the silicon nitride film/silicon oxide film test pieces used were 160 O.11 equivalent to those used in Example 1. The treating condi tions, etc. were pursuant to Example 1 too. The results are 161 O.13 tabulated in Table 18. O.04 162 O.15 TABLE 1.8 163 O.17 O.12 Sample IPA SiN Etch- SiO, Etch 164 O.21 No. (%) Inhibitor rate (nmmin) rate (nmmin) O.15 16S O.28 18O O (not used) O.6 S.6 O.28 (used) O.1 S.6 181 5 (not used) 0.7 4.7 (used) O.3 4.7 182 10 (not used) O.6 3.8 0101 From the results of Table 16, it has been found that (used) O.3 3.8 Sample 160 having no organic solvent (0%) added to it shows 183 2O (not used) O.S 2.8 the lowest etch selectivity upon addition of the inhibitor, and (used) O.S 2.8 184 30 (not used) 0.4 2.O the etch selectivity grows high in proportion to the content of (used) 0.4 2.O the organic solvent, while the etch selectivity of Sample 165 185 50 (not used) O.3 1.2 of 50% in concentration is the same regardless of the presence (used) O.3 1.2 or absence of the inhibitor. US 2015/0279.654 A1 Oct. 1, 2015 43

TABLE 18-continued (2) H Sample No. Etch Selectivity ka-y 18O O.11 O.O2 181 O.15 CO O.O6 182 O16 O.08 183 O.18 O.18 wherein, R Stands for hydrogen or an alkyl or alkylene 184 O.2O group having 1 to 4 carbon atoms, X stands for a func O.2O tional group capable of becoming an anionic ion, and in 185 O.25 O.25 stands for a natural number of 2 or greater; and

(3) 0105. From the results of Table 18, it has been found that Sample 180 having no organic solvent (0%) added to it shows the lowest etch selectivity upon addition of the inhibitor, and the etch selectivity grows high in proportion to the content of the organic solvent while Sample 183 having an organic COA-4 ex X4 X3 solvent concentration of 20% shows the same etch selectivity regardless of the presence or absence of the inhibitor. It has also been found that Samples 184 and 185 having 30% and wherein Rs stands for hydrogen or an alkyl or alkylene 50% organic solvent concentrations show etch rates further group having 1 to 4 carbon atoms, and X, and X stands decreasing in proportion to the content of the organic solvent. for a functional group capable of becoming an anionic ion. APPLICABILITY TO THE INDUSTRY 2. The treating solution for electronic parts as recited in claim 1, wherein said aqueous solution has a pH value of 2 to 0106 The additive of the invention, and the treating solu 6. tion to which it is added, can preferably be used in the process of producing electronic parts such as semiconductors like 3. The treating solution for electronic parts as recited in memory devices, operator devices, logical operator devices claim 1, which contains hydrofluoric acid in an amount of or other LSIs, and display devices such as liquid crystal 0.001 to 50 mass %. display devices and organic EL display devices. In particular, 4. The treating solution for electronic parts as recited in the additive and treating solution of the invention are very claim 1, wherein said hydrofluoric acid is obtained by disso useful for the case where there is the selective protection of lution of a water-soluble fluoride salt. nitrogen-containing silicon compounds needed in the process 5. The treating solution for electronic parts as recited in of producing devices having a structure in which there is a claim 1, which contains a cyclic compound having an occu nitrogen-containing silicon compound present in combina pied area Smaller than a naphthalene ring. tion with an oxygen-containing, carbon-containing silicon compound. 6. The treating solution for electronic parts as recited in claim 5, wherein said cyclic compound is represented by the following formulae (4), (5), (6) or (7): 1. A treating solution for electronic parts, which is an aqueous solution containing one or two or more of anionic Surface active agents having the following formulae (1), (2) and (3): (4) a-y (1)

wherein a1, a2, as aa, and as stands for any one or more of OC a carbonatom, a nitrogenatom, an oxygenatom, a Sulfur atom and a phosphorus atom, these 5 constituting ele ments form a cyclic structure by having any chemical wherein R, R2, and R Stands for hydrogen or an alkyl or bond between neighboring constituting elements, pro alkylene group having 1 to 4 carbon atoms, and X viding a cyclic compound showing aromaticity under stands for a functional group capable of becoming an conditions under which it is used, ora, a2, as a, and as anionic ion; may further bond to a functional group; US 2015/0279.654 A1 Oct. 1, 2015 44

wherein d, d.d. d4, ds, d, d7, and ds stands for any one (5) or more of a carbon atom, a nitrogen atom, an oxygen b1-b2 M V atom, a Sulfur atom and a phosphorus atom, these 8 b6 b3 constituting elements form a cyclic structure by having V b5-b4. any chemical bond between neighboring constituting elements, providing a cyclic compound showing aroma wherein b,b,b,b,bs, and be stands for any one or more ticity under conditions under which it is used, or d, d. of a carbon atom, a nitrogen atom, an oxygen atom, a da, d4, ds, d, d7, and ds may further bond to a functional Sulfur atom and a phosphorus atom, these 6 constituting group. elements form a cyclic structure by having any chemical bond between neighboring constituting elements, pro 7. The treating solution for electronic parts as recited in viding a cyclic compound showing aromaticity under claim 5, which contains said cyclic compound in an amount conditions under which it is used, orb,b,b,b,bs, and of 0.001 mass % or greater. be may further bond to a functional group: 8. The treating solution for electronic parts as recited in (6) c2 claim 1, which contains saidanionic Surface active agent in an 11 N. amount of 0.001 mass % to 2 mass %. \ 9. The treating solution for electronic parts as recited in claim 1, wherein said aqueous Solution contains a buffer c8; - y comprising a weak acid and an alkali species. Y, -c6 10. The treating solution for electronic parts as recited in claim 1, which further contains an organic solvent miscible wherein c1 c2cs, ca, cs, co, c.7, cs and costands for any one with water. or more of a carbon atom, a nitrogen atom, an oxygen atom, a Sulfur atom and a phosphorus atom, these 9 11. The treating solution for electronic parts as recited in constituting elements form a cyclic structure by having claim 1, which is used with an electronic part including a any chemical bond between neighboring constituting structure having a nitrogen-containing silicon compound as a elements, providing a cyclic compound showing aroma component material, and a structure having a nitrogen-free ticity under conditions under which it is used, or c, c. silicon compound as a component material. cs, ca, cs, co, c.7, cs and co may further bond to a func 12. A process for producing electronic parts, which tional group; includes a step of etching or cleaning an electronic part, using (7) the treating solution for electronic parts as recited in claim 1. 13. The process for producing electronic parts as recited in claim 12, in which said electronic part includes a structure having a nitrogen-containing silicon compound as a compo nent material, and a structure having a nitrogen-free silicon compound as a component material. k k k k k