ELECTRONIC CHEMICALS ABOUT HERAEUS
A globally leading technology group, Heraeus is With technical expertise, a commitment to excellence, headquartered in Hanau, Germany. Founded in a focus on innovation and entrepreneurial leadership, 1851, it is a family-owned portfolio company which we are constantly striving to improve our performance. traces its roots back to a pharmacy opened by the We create high-quality solutions for our clients and family in 1660. Today, Heraeus combines businesses strengthen their long-term competitiveness by in the environmental, energy, electronics, health, combining unique material expertise with leadership mobility and industrial applications sectors. in technology.
In the 2018 financial year, Heraeus generated revenues of € 20.3 billion with approximately 15,000 employees in 40 countries. Heraeus is one of the top 10 family-owned companies in Germany and holds a leading position in its global markets.
About Heraeus Epurio LLC
Heraeus Epurio LLC is an award-winning specialty We provide quality turnkey service and are known in chemicals producer that develops Photo-Acid our industry as the reliable partner in development, Generators (PAGs), Polymers, Monomers, and from molecule to multi-tonne scale, to after-sales Crosslinkers for the semiconductor, display, and technical support. electronic and aerospace industries.
We are experts in producing materials with low trace metals, while also having extensive experience in synthesizing a wide variety of organic compounds.
2 PHOTO ACID GENERATORS
Heraeus Deep UV PAG
Based on 30 years of experience in producing Most of these products are available in Ultra-Pure electronic-grade photoactive materials as (UP) quality with purity above 99.5% and content Daychem Laboratories in Dayton (OH), Heraeus has of all 26 metals below 10 ppb. This makes even put together selected chromophores together conventional chemistry available for new frontiers in with vintage acids to create different classes of resist resolution. unique products for critical layer resists in highest resolution.
Heraeus Ionic PAG Strong bulky acid
Product Name Chemical Structure Properties Features
Strong acid generation m.p. 128~9°C PA-253 ArF High solubility (>20% in PGMEA)
Heraeus Ionic PAG C1 acid
Product Name Chemical Structure Properties Features
TPS-C1 Strong acid(C1) generation m.p. 76~78°C Deep UV
TTBPS-C1 Strong acid(C1) generation m.p. 164~165°C Deep UV
DTBPIO-C1 Strong acid(C1) generation m.p. 104~105°C Deep UV
Regular product Ionic PAG 3 Ionic PAG
Heraeus Ionic PAG – N3 acid
Product Name Chemical Structure Properties Features
TPS-N3 Strong acid(N3) generation m.p. 104~105°C Deep UV
TDPS-N3 Strong acid(N3) generation m.p. 83~85°C Deep UV
TBPDPS-N3 Strong acid(N3) generation m.p. 114~116°C Deep UV
TBPTMS-N3 Strong acid(N3) generation m.p. 177~178°C Deep UV
TBPTO-N3 Strong acid(N3) generation m.p. >240°C Deep UV (PA-289)
Heraeus Ionic PAG – Nf acid
Product Name Chemical Structure Properties Features
Low diffusion strong acid(nonaflic acid) TPS-Nf Deep UV generation m.p. 84~88°C
TBPDPS-Nf Low diffusion strong acid(nonaflic acid) Deep UV (PA-271) generation m.p. 131~137°C
TBPTMS-Nf Low diffusion strong acid(nonaflic acid) Deep UV (PA-282) generation m.p. 174~176°C
DTBPIO-Nf Low diffusion strong acid(nonaflic acid) Deep UV (PA-233) generation m.p. 175~177°C
Strong acid(N1) generation m.p. DTBPIO-N1 Deep UV 153~155°C
Regular product
4 Heraeus Ionic PAG – other acids
Product Name Chemical Structure Properties Features
Strong acid (perfluorobutane disulfonic BTPSPFBDS Deep UV acid) generation m.p. 157~159°C
Weak acid (o-trifluoromethylbenzenesul- TPS-TFMBS Deep UV fonic acid) generation m.p. 156~157°C
Weak acid (o-trifluoromethylbenzenesul- DTBPIO-TFMBS Deep UV fonic acid) generation
Weak acid (camphorsulfonic acid) genera- DTBPIO-CS tion Deep UV m.p. 215~217°C
Strong acid (perfluorobutane disulfonic DTBPIOPFBDS Deep UV acid) generation m.p. 175~176°C
Heraeus Non-ionic DUV PAG
Product Name Chemical Structure Properties Features Remarks
White powder Strong acid (triflic MDT Deep UV acid) generation m.p. 88~89°C
White powder Low diffusion strong PA-229 acid (nonaflic acid) Deep UV generation m.p. 54~56°C
Regular product NON-ionic PAG 5 HERAEUS I-LINE AND BROADBAND PAG
Following the growing market demand for highly Purity is according to the proven electronic grade sensitive, high solubility i-line PAG for various quality of Heraeus, and most of the PAGs are scaled chemical amplified resist applications, Heraeus up cost-effectively in production to deliver up to developed a set of i-line, broadband and even g-line tons quantity per year, making them also attractive products. for cutting-edge devices for memory chips, advanced packaging and display resists.
Heraeus Standard i-line PAGs
Product Name Chemical Structure Properties Features
White powder NIT Strong acid (triflic acid) generation i-line m.p. 210~214°C
White crystalline powder. Low diffusion NIN Strong acid (nonaflic acid) generation i-line m.p. 148.5~149.5°C
Light-yellow powder ILP-110 Strong acid (triflic acid) generation i-line m.p. 113~114°C
Low diffusion strong acid (nonaflic acid) ILP-110N i-line generation m.p. 122~124°C
Light-yellow powder ILP-118 Strong acid (triflic acid) generation i-line m.p. 66~68°C
Regular product
6 i-line PAG UV spectra of i-line PAGs
i-line PAGs
0,6
0,5
0,4 NIT
ILP-110N
0,3 NIN Absorbance ILP-118 0,2 ILP-110
0,1
0 300 350 400 450 500 Wavelength (nm)
* Sample concentration: 0.001% in PGMEA or ACN
Heraeus i, g, h-line PAGs
Product Name Chemical Structure Properties Features
Yellow powder i, h-line ILP-113 Strong acid (triflic acid) generation broadband m.p. 125~126°C
White powder HTPG-104S Strong acid (HCI) generation i-line m.p. 143~145°C
Orange powder i, h, g-line PA-223 Strong acid (triflic acid) generation broadband m.p. 146~147°C
Regular product i-line PAG 7 PAG UV spectra for i, g, h-line PAGs I, g, h-Line PAGs
1
0,9 ILP-113 ILP-191 0,8 PA-223 0,7 HTPG-104S
0,6
0,5 Absorbance 0,4
0,3
0,2
0,1
0 250 300 350 400 450 500 Wavelength (nm)
Formulation and relative i-Line UV absorption sensitivity i-line (365 nm) h-line (405 nm) g-line (436 nm) Transparency Window
NIT
NIN ILP-118 ILP-110 ILP-110N HTPG-104S PA-223 ILP-110 ILP-113 ILP-191 ILP-110N
ILP-118
ILP-113 NIN NIT
ILP-191
PA-223 Less Sensitive Each resist has the same molar equivalent of PAG 300 350 400 450 500
Wavelength (nm) Resist consists of 30%-protected PHS, PAG, and TEA as quencher in PGMEA
8 UV SOLUBILITY
Solubility in PGMEA, %(w/w, RT)
NIT NIN ILP-110
ILP-191
PA-223 ILP-113 ILP-118 48% solubility ILP-110N
0 5 10
Solubility Increase
Patterning test: Positive tone chemical amplified resist
Water-insoluble system PAG Water-soluble system hv
H+ ∆ Resist layer Resist layer Substrate Substrate Substrate Substrate
Patterning test results
NIT NIN ILP-110 ILP-191 ILP-113 ILP-118
Coating Thickness Exposure ~1um by spin coating / 10sec (1sec + about 7.0 mJ) / Development SOB condition: 110oC, 60sec Light source: LED i-line / No PEB 2.38% TMAH, 23oC, 60sec PATTERNING 9 Heraeus Weak Acid PAGs
According to the market demand of weak acids Highest purity and quality consistency is a given for sensitive resin systems, Heraeus offers proven also for this product range. sensitive chromophore and weak-acid combinations as cost-effective alternatives to existing systems.
Heraeus Non-Ionic weak acid PAGs
Product Name Chemical Structure Properties Features
Yellow powder PA-480 Weak acid (sulfonic acid) generation i, h, g-line m.p. 143~145°C
Yellow powder PA-411 Weak acid (tosylic acid) generation i, h, g-line m.p. 136~139°C
Yellow powder PA-298 Weak acid (sulfonic acid) generation i, h, g-line m.p. 93~95°C
White powder PA-528 Weak acid (tosylic acid) generation i-line m.p. 134°C
10 UV spectra for weak acid PAGs
Weak Acid PAGs i-line (365 nm) h-line (405 nm) g-line (436 nm) 1 Transparency Window 0,9 PA-411
0,8 PA-597
PA-480 0,7 PA-528 0,6
0,5 Absorbance 0,4
0,3
0,2
0,1
0 250 300 350 400 450 500 Wavelength (nm)
* Sample concentration: 0.001% in PGMEA or ACN
11 HERAEUS CROSSLINKERS
Heraeus has a long tradition of manufacturing Heraeus define the new standard in the semicon glycoluril-based crosslinkers in highest purity for industry. Various chemical modifications have semicon resists. This is why processes have been significantly lowered the sublimation tendency. developed and scaled up to reduce or remove contaminations of formaldehyde and methylene Furthermore, Heraeus developed certified methylene chloride. chloride-free versions of crosslinkers to comply with international regulations against hazardous, Today the low-metal contamination and the halogenated materials, and to provide safe and methylene chloride-free (MCF) products from environmentally-friendly products.
Product Name Chemical Structure Properties Features
White crystalline powder m.p. 107~113°C PL-1174 Available methylene chloride-free (MCF) and UP
Colorless liquid TBGU Available methylene chloride-free (MCF) and UP
White powder m.p. 87~89°C PLPM Available methylene chloride-free (MCF) and UP
White powder m.p. 136~138°C PL Phenyl Methyl Available methylene chloride-free (MCF) and UP
Regular product
Comparison of TGA
100
80
PL1174 PL Phenyl Methyl 60 PLPM Weight %
40
20
0 0 130 230 330 430 Temperature (°C)
12 Comparison of DSC
4 PL1174 PL Phenyl Methyl 3 PLPM
2 Heat flow
1
0 30 50 70 90 110 130 150 Temperature (°C)
Decomposition temperatures
TBGU
1% wt loss PL Phenyl Methyl 5% wt loss >90% wt loss PLPM
PL 1174
0 100 200 300 400 Temperature (°C)
Solubility for crosslinkers
Solubility into 100 mL of PLPM (-MCF) PL Phenyl Methyl PL1174 TBGU a
Water 7.7 g <0.3 g 11.8 g ~6 g
Methanol 46 g 3.4 g 22.6 g miscible
IPA 10 g <2 g <2 g miscible
EL 25 g <2 g 6 g miscible
PGMEA 10 g <2 g <2 g miscible
PGME 10 g <2 g <2 g miscible
13 HERAEUS MONOMERS: ACRYLATE
Coming from long experience of critical layer From UP grade for new critical layer developments polyacrylate-based resists, Heraeus developed and to high-end memory and logic chips-related photo scaled up a number of monomers with sterically materials such as PR, BARC, and hardmask applica- hindered groups. tions, where cost and volume availability are important factors, we offer the entire product range.
Product Name Chemical Structure Properties Features
Photorelated MNLMA White powder m.p. 74~77°C material for ArF
Photorelated NMLA White powder m.p. 101~102°C material for ArF
Photorelated MAdMA Colourless liquid material for ArF
Photorelated ECHA Colourless liquid material for ArF
BARC 9-AMM Yellow powder m.p. 86~88°C Deep UV resist
HERAEUS THERMAL ACID GENERATORS
With thicker film resist demands, more and more An IP-free set of products with different acid- formulations contain thermal acid generators to releasing temperatures is available from Heraeus. enable final curing during post-baking. Semiconductor-grade purity and effective costs are mandatory in the final application.
Product Name Chemical Structure Properties Features
White powder 4.5% (w/w) in PGMEA TA-101 m.p. 101~102°C
White powder 2.5% (w/w) in PGMEA TA-102 m.p. 126~127°C
Regular product 14 Product Name Chemical Structure Properties Features
White powder 5% (w/w) in PGMEA TA-103 m.p. 101~102°C
Acid generation – temperature by heating
60 sec. heating60 sec. heating 180 sec. heating180 sec. heating
TA-101 TA-101 TA-101 TA-101
TA-102 TA-102 TA-102 TA-102
TA-103 TA-103 TA-103 TA-103
110°C110°C 130°C 130°C 150°C 150°C 110°C110°C 130°C 130°C 150°C 150°C
Formulation Test TAG + Fluorescein (Acid indicator) Coating on glass PHS-EVE (resin) baking on hot plate PGMEA (solvent) Measuring transmittance
HERAEUS POLYIMIDE PRECURSORS
Heraeus can toll manufacture Polyamic Acids and and can safely handle all major solvents, diamines, other PI precursors to suit your needs. We have the and dianhydrides. capacity to produce an output of 2 tons per day,
Product Name Chemical Structure Properties Features
Used as coatings in High dielectric stability at Polyamic acids flex circuits, display, battery high temperatures, (PAA) for applications, photovoltaic chemically resistant and Polyimides and anywhere PI films are can be made colorless needed
PMR Used in composites for (Polymerizable Various diamine dianhydride Used in temperatures high-temperature aerospace Monomeric mixtures over 350°C applications Reactants) Resins
Regular product 15 Custom synthesis service Purification technology Heraeus provides all kinds of chemical compounds based High-end photoresist applications in semiconductors require on the customer’s requirements, using our high-level super-low chemical impurity and metal ions content. synthesis technology and long experience in electronic Heraeus has begun producing ultra-purification-grade materials. Rapid and smooth transition from g-scale to products for advanced semiconductor photoresists. kg-scale is provided. Please get in touch with our sales Our new production facility, equipped with full clean room
team. environment, will operate in 2021. EN/01.2021/www.data-graphis.de
HANAU, DE DAYTON, USA SUWON, KR TOKYO, JP SHANGHAI, CN TAIPEI, TW
n Headquarters: Hanau, Germany n Production : Dayton, Ohio, USA n Sales offices: Heraeus Materials Technology Taiwan Ltd., Taipei, Taiwan Heraeus Shanghai, China Heraeus Korea, Suwon, South Korea Heraeus K.K., Tokyo, Japan Heraeus Epurio LLC, Dayton, Ohio, USA The data given here is correct for January 2021 and is subject to change.
[email protected] heraeus-epurio.com