MXPA97003797A - Promoters of accession of substance photoendurecible not aminic for applications microelectroni - Google Patents

Abstract

A method for providing a silylated substrate having improved adhesion to polymeric films is described, the method comprising reacting at least one organosilane compound having at least one alkylsilyl moiety therein and at least one hydrolysable group capable of reacting With the substrate to silylate the substrate, hydrolyzable byproducts of the reaction, if any, have a pH less than or equal to

Description

PROMOTERS OF ADHESION OF SUBSTANCE PHOTOENDURECIBLE NOT AMINIC FOR MICROELECTRONIC APPLICATIONS FIELD OF THE INVENTION The invention is directed to the treatment of semiconductor substrates before, of application of photoresistible substances thereon during the manufacture of < 1? sposi r i vos microeleet rom cos. u BACKGROUND OF THE INVENTION The microelectronics industry influences all aspects of modern economies. At the center of this industry are the microeligible devices commonly known as integrated circuits. Improvements in design and ma- ter a.es in recent years have increased the performance of integrated circuits from those containing a few thousand transistors to those of f) millions of transistors in approximately the same circuit size integrated. It is expected that in the near future these devices will contain billions of transistors in this ir-sized integrated circuit. The minimization of the integrated circuit, in order to promote greater functionality per unit area, has put < There are also demands on the design, as well as on the materials and chemical agents used in the manufacture of the integrated circuit. An important aspect of the manufacture of these devices includes the application to the substrate of photoactive films, that is to say, f-o-t or hardenable substances. 5 Photo-darkening substances are applied to all levels of masking in the manufacture of microelectronic devices. For example, masking levels of 20-25 can be used during the production of food digestion or s. Photocells have been used in the production of innovative devices throughout the history of the manufacture of these devices. The first fabrications of devices used photolithographic techniques in which they were placed or applied as A film of photodegradable substance was coated on such a silicon substrate, reflected with light, and revealed in a desired pattern with chemical developers. The resulting pattern was used as a selective mask in subsequent operations such as the Lomeo implant, modeling subjacent substrate, metallic ironing, as well as other different steps during the manufacture of these di positive. The initial application methods of photoresistors presented problems including poor coating of the photoresist on the : > substrate, loss of the pattern of loss of portions of the photocurable substances on the part of the chemical developers, as well as "recess", of the photo-resistant substance with developer-is chemical, Rl re-occur when a developer- aqueous or organic material along the interface between a polar substrate and the photocurable substance to cause the photocurable substance to detach from the substrate. The above problems have been eliminated primarily when hexarnetii disilazane ("HMDS") has been used to pretreat, ie, "sizing" the silicon substrates prior to application of the photoresist substance. It has been found that the sizing of the substrates with HHDS promotes better photoreeistor coatings, provides more uniform photocurable films on the substrates, reduces gaps in these films, as well as reduces recessing and lifting of the photocurable film during development. It is believed that these improvements are due to chemical reaction of HMDS with hydrogen-bound water molecules on the surface of the substrate. As a result, it has greatly improved the performance of the devices with HMDS, thereby promoting the adoption of HMDS as a normal pre-mouse by the manufacturers. During the sizing of silicic substrates with HMDS, the initial chemical reaction of the HMDS with water molecules bound to hydrogen produces ammonia, t rirneti isi lanol and hexarnetiidisi loxane. Subsequent reaction of HMDS with droxyl groups and oxide on the surface of the substrate produces a substituted tpmethysiloxy, i.e., silylated surface. It is believed that the silled surface reduces the number of polar surface groups, reduces the surface energy and provides an essentially monomolecular organic coating on the substrate which is compatible with organic photoharmonic substances. H. Ya azawa, Collo ds And Surfaces, vol. <;? , pp. 133-145, (1984), describes that the interaction between the organic photocurable substance and the substrate surface with sizing is probably hydrophobic in nature. The hydrophobic t-rimethylsilyl groups on the substrate also repel polar groups such as those present in water and aqueous developers to avoid rework at the substrate interface - photocurable substance. As is known in the art, the production of a silica surface occurs when a reactive silicon compound in the silylating agent reacts with a protic species on the surface of the substrate to produce a silicon compound or the pro-species species. , as well as a protonated unattached byproduct. The degree of surface silylation achieved during sizing with materials such as HMDS can be calibrated by measuring "surface contact angle". As it is known, the greater the contact angle, the greater the magnitude of silylation. It is also known that the contact angle of the surface can be measured by focusing a contact angle goniometer available commercially on a drop of water placed on the silylated substrate.A high contact angle indicates that a greater number of silylating groups such as The tprnet il sil Lio groups are bonded to the surface of the substrate .. Previous observations by 1. L. Nis ie, "Simple Techimque to flnalyse Conditions That Affect Subinicron Photoresist Adhesion", KTI Microelect onics Seminar -inter * face "88, pp. 233-24 ?, (1988), ("N1STLER") and by U. Mo reau, Semiconductor * Ithology: Pr-inciples, Practices, and Materials, Plenuin Press, New York, (1988), ("MOREAU") , on substrates such as silicon, silicon dioxide and silicon trio, indicate that a contact angle of b5-8b degrees is desirable, since dehydration of the photocurable substance can occur above and below these angles. contact. Improvements to using HMDS to "apply * capture" to a subst ato include "Application of pure HMDS liquid, HMDS diluted with one or more solvents, and steam sizing application - where HMDS vapors are applied a The surface > 1e a substrate. As is known in the art, steam sizing * can be performed by treating batches of wafers in an oven, or by treating individual wafers in an in-line rail system. Both methods involve heating the wafers under vacuum, after which HMDS steam is introduced onto the wafers. Generally, the sizing allows the application of films of organic-based photo-solid substance to the substrate prepared in subsequent steps. A film of acceptable photogenic substance is a uniform continuous eluate that does not exhibit voids, edge curl, ballooning, bubble formation, lifting or "puffing" during exposure, and does not exhibit significant detachment or rejection during chemical development. Steam sizing is a preferred method for pretreatment of substrates in the manufacture of high density microelectronic devices. HMDS is the most popular agent for wafer sizing. Other agents that have been used for sizing substimes include t r net l silyl diethylamine (TMSDEA) and t pmethylsilyldimoty sheet (TMSDMfl). Rl sizing with HMDS, TMSDEA, and TMSDMA, however, can generate basic byproducts of ammonia, diethylamine, and direthylamine that can negatively affect the high resolution of photogenic substances. The high resolution photoresist substances are typically aqueous or negative positive developer compositions that have been chemically amplified. These photocurable substances, by exposure to radiation such as photons, electrons or ions at wavelengths of a few nanometers (x-rays) up to about 450 n, generate smaller amounts of compounds such as diazonaphthoquinones, dodecyl salts, diazacetates and diazoacetones that may be present in the composition fotoend? recihl. These acids are useful for performing reactive functions during the subsequent steps in the manufacture of the integrated circuit. These reactive functions include, for example, hydrolysis of protective groups, molecular weight modulation, and / or entanglement to increase the molecular weight and density of the photocurable substance. These reactive functions typically occur after exposure of the photocurable substance to radiation in a subsequent exposure of the baking step prior to the development of the photocurable substance. Recently, it was discovered by S. MacDonald et al., Proc. SPIE, 1466; 2-7 (1991), by U. Hinsberg et al. In Proc. SPIE, 1672, 24-32 (1992) and U. Hmsberg and others in PM E Preprint, ACS National Meeting, San Francisco, CA, (1992), that the acids generated in the photocurable substance can react with trace amounts of residual amines, ammonia and other byproducts that have nitrogen generated by the sizing and that can remain on the surface of the substrate and in the atmosphere of manufacturing that surrounds the substrate. These by-products can conveniently neutralize the acids generated by the photo-hardenable substance and thereby adversely affect the quality of the photo-hardenable substance. The high-resolution photocurable substances typically used in the manufacture of high-density microelectromechanical devices are curable in the far-away, chemically-amplified (DUV-CARS). Ammonia and amine-containing products generated during application of "-" may soon be especially harmful to DUV-CARS. It has been reported by MacDonald et al., Proc. SPIE, 1466; 2-7 (1991), that a 15 minute exposure of DUV-CAR photo-hardening substances to 15 pprn of amine causes rolling or creaming. The presence of basic byproducts and volatile contaminants of clean rooms that are ammonia or amines or byproducts of amine has been reported by 0. Muller et al. In Solid State Technology, pp. 61- / 2, Septembre 1994, which neutralize acid groups in the surface of the receptor causing a film on the surface of the photocurable substance ("cream"), a control of gradient line width and, therefore, a control of critical dimension ("CD") decreased, decreased device performance and decreased process reliability. Different methods have been introduced to address the inconvenient effects caused by compounds and byproducts of amine and ammonia. Overlays that provide a barrier coating on the photoresist to avoid contact of the acids generated in the photoresistible substance with residual ammonia and amine byproducts produced during sizing with compounds such as HMDS are recommended by the manufacturers of resistors such as TBM. , OCG, Shm-Etsu and JSR in their application literature. It has been shown by Berro et al., Microcontarnination, p. 37 (Tune 1993), that volatile amines or ammonia form crystal-like amine salts on the surface of the wafers. The installation of ionic acid filters or air purifiers with solutions in the manufacturing facilities of the air supply / waste recirculation system has also been used to reduce ammonia contamination. The removal of ammonia carried through the air by filtration with activated charcoal has also been attempted. However, these methods are expensive and have marginal success in the control and removal of contaminants of arnoni aco / arnin. Therefore, the need for more reliable and efficient methods to reduce the amount of arnomaco / arnin-type contaminants generated during the manufacture of microelectronic devices continues.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the invention, it has been discovered that selected organosilane compounds can be employed to silylate a substrate to impart a substantive coating equivalent to that obtained with HMDS, but can generate conventional by-products such as ammonia, or amine-like compounds. Substrates that can be silled include, but are not limited to, single crystal silicon, silicon dioxide, silicon dioxide, silicon truro, aluminum, aluminum oxide, copper, copper oxide, titanium, titanium nitride, tungsten. titanium, silicon phosphorus boron glass, LO rotatable glass, and catfish. The application of selected organosilane compounds does not interfere with the effective functioning of acids generated in photogenic substances, including chemically amplified ones. The application of these selected organosilane compounds also promotes uniform coating and bonding of photogenic substances to the substrate. The invention employs selected organo-silanes for silting the surfaces of substrates such as silicon for To promote effective application of a layer of photo-hardening substance on those surfaces. The invention solves the long-standing problems in the art associated with generation of ammonia and byproducts containing am a generated during application of sizing to the L5 substrates. The invention also substantially eliminates over-sizing and up-sizing to allow a controllable, reproducible sizing, with equipment currently available with little or no modification and in shorter periods with improved material economy. In accordance with the invention, a method is described for substantially eliminating contamination of silylated substrates with basic by-products to produce improved binding of polymeric films such as photoresist substances to a substrate surface. The method 5 comprises reacting at least one organosilane compound, especially trialkylsilyl compounds and dialkylsilylene compounds, with a substrate to silylate the substrate. The organosilane compound includes leaving, hydrolysable groups which are capable of generating byproducts having a pH of less than 7. Different photoresist substances can be applied to the silylated surfaces produced by the selected organosilines employed in the invention. These photohardenable substances include, for example, those compositions containing such compounds as polyvinyl, 1 phenol, polyhydroxystyrene, pol (t-butylcarboxy) -styrene, polyurea, polybutoxystyrene, polyphenols, novolac. formaldehyde, and polyacrylic esters, as well as mixtures and copolymers, with the same, with interlacing materials, such as cyanurates, and a photomitator such as orno salts, diazonafen coughs, and azides. Especially useful organosilanes for use as silylating agents in the invention are the tialkyl silanes of the formula: where X is 0, or MRl; Y is 0, CH2, CHR, CHOR, CRR or NRi; R is any hydrogen, saturated C 1 -C 4 alkyl, especially saturated C 1 -C 2 alkyl; saturated cyclic alkyl of C4-C6, essentially saturated cyclic alkyl of Ce; more Ci-Cβ-saturated alkyl, especially more saturated alkyl of Q 2 -C 4; unsaturated cyclic alkyl of C 4 -Ce, especially unsaturated cyclic alkyl of C 5 -Ce; C2-C10 fluorinated hydrocarbon alkyl, especially fluorinated hydrocarbon alkyl of C2-C3; fluorinated alkyl, especially fluorinated C 1 -C 2 alkyl; fluorinated cyclic alkyl of C 5 -Ce, especially fluorinated cyclic alkyl of Cs -C 6; t p C 1 -C 3 -alkylsiloxy, especially M 3 SiO; tr-ialkylsilyl, especially Mß3 i; C1-C12 alkoxy, especially C1-C2 alkoxy; phenyl, phenethyl, acetyl, 1-propanol, 2-propanol, alkylketones such as 1- and 2-alky1-ketones of C2-Ce, especially acetyl-2-pr-opaneyl; esters of alpha-acetyl of C3-C6, especially ethylacetyl; and R1 is any of hydrogen, methyl, rifluoromet Lyo, trifluoromethylethyl, or rimethylsilyl. Particularly useful palletizing agents include those of the formula: Wherein R2 is any of saturated alkyl such as alkyl of i-, especially methyl, ethyl; unsaturated alkyl such as unsaturated alkyl of O2 ~ Cß, especially vimlo, aillo; cyclic alkyl such as or C3-Ce cyclic alkyl, especially cyclopentyl, cyclohexyl; 5 unsaturated cyclic alkenes such as unsaturated cyclic alkenes of Ct, -Ce, especially cyclopentenyl, cyclohexelo; fluoroalqui such as fluoroal ui 1 -alqu lo Ci-C, especially t rifl uoroeti lo; faith, faith what is fluoridated, such as rent faith, what is fluorinated and fluorophene, especially pentaf1 ororophe; alkyl ethers such as ethers to the ethers of the LCOI ileum and alkyl LCOS teres of propylene glycol, especially ethyl ether of ethylene glycol; alkyl ketones such as C2-C8 alpha-ketoalkenes, especially netacroyl; saturated fluorinated alkyl ethers such as or perfluoroalkyloxy-C 3 -C 5 alkyl, especially full fluoro et al. Fluorinated unsaturated alkyl esters such as l-per lor-oalqui 1-1-alkox et llenos, especialment 1- t rifl? oromet? i-l-ethox? et lono. Other t ñaiqui lysilanes that are particularly useful in the invention include those of the formula: Where R3 is any saturated alkyl or straight or branched chain alkyl, especially methyl; and saturated fluoroalkyl such as t r *? f luoroalkyl, especially t r *? fluo rome Lio. Particularly useful partial solids for use as silylating agents in the invention include 0-trirnetiiyl-yl acetate (OTMSA), 0-t-prnethyl-lyl-propionate (OTMSP), butyrate of 0-ri and lls. What is t rirnethylsilyl (TMTFA), tnmethylmethoxysilane (TMMS), N-methyl-Nt r? met? is? l? tr? fl uoroacetanide (MSTFA), acetylacetone of 0-t prnet 11 sil (OTMAA), isopropenoxy trimethelsilane (IPTMS), b? s (t pmetiisi li Dtpf luoro-acetarnide (BSA), rnetil acetate r ld? rnet 11 -ketone (MTDA), tprnet lie tox isi (TMES) TarnbLen can be used as silylating agents in the invention the dial if lanos where the silicon volume is attached to the hydrolyzable reactive groups which, by reacting with the substrate, provide an organosi compound over the substum while at the same time generating substantially only its acidic or neutral products Particularly useful dialkylsilanes include dirnetiidi netox silane and dirnetiidiacetoxysilane The organolens used in the invention can be applied to the substrate by means of steam, liquid or solutions containing the organo-eilane at a temperature of approximately 12 ° C ambient temperature and pressures of approximately atmospheric pressure at least of approximately L torr. The organosiline can also be mixed with a photocurable substance and the mixture applied to the substrate to provide a uniform film on the substratum. In another aspect of the invention, a substrate is provided that has adhesion for polyester coatings, such as photocurable substances, which is at least equal to the adhesion achieved by HMDS silylating agents.

DETAILED DESCRIPTION OF THE MODALITY Generally, the selected Lanos organos employed in the invention have in their molecular structure at least one hydrolysable reactive group which is attached to a silicon atom. These organosilanes are substituted monomers of alkylsilicon containing at least one salient hydrolysable group bound to a SLILCLO atom. The leaving group is a chemical moiety such as acetate, carboxylate, enoL, alkoxide, sulfate or amide. By * reacting the organosilane with the substrate during the sizing application, the organosilane can produce acidic or neutral reaction byproducts depending on the specific hydrolyzable leaving group. These by-products can be described by means of the Bronsted-1 system and the conjugated acids of the organosilane molecule. The classical definition of Arhemus applied to by-products would be that of molecules with? I, in aqueous solutions, of less than, or approximately equal to, 7. The selected organosiines employed in the invention can be applied pure as liquids, or as solutions in organic solvents such as xylene or PGMEA. The selected organosilanes can also be used as mixtures with one another. These selected organosilanes can also be applied pure as vapors, or as mixed vapors with gaseous vehicles such as nitrogen and inert gases such as argon. During application, the selected organosilanes are injected as liquid or vapor into a low pressure silicone area through an opfium, or by spray application of the organosilane in a hot area where the The resulting vapor is transported by inert gas or vacuum to the substrate to be treated. Although it is not intended to be bound by theory, it is believed that the hydrogen ion will occur during the sizing application of a substrate as in the reaction 1: 20 R R I I R-Si-X - HO-Z R-Si- O-Z + XH: D z > Where R = methyl 7, - substrate composition X = leaving group As shown in I, during the sizing application of a substrate such as silicon, the organosilanes used in the invention appear to react with the substrate to form a surface layer of alkylsilyl groups, especially dirnet and leyl groups approximately one molecule thick on the Substrate surface. Although it is not intended to be bound by theory, it is believed that the leaving group of the organosium, during the reaction with surface water bound to hydrogen, hydroxyl groups. or similar reactive species on the surface of the substrate accept a proton to produce, for example, a t-pmet ilsyl L-group attached to the substrate. It is also believed that the reaction produces byproducts such as acids, alcohols, ketones and amides which have neutral or acidic properties, depending on the leaving hydrogenation group in the organosilane. These by-products can be represented by II: And H-X-Z-R Where X is 0, NRi or CH2; And it is 0 or NRl; Z is C or S --- 0, and R is H, Ci-C saturated alkyl, unsaturated C2-C8 alkyl, Ct alkyl, unsaturated cyclic, fem Lo, fluoral chyl C? ~ Cβ saturated, fluor containing fem lo such as tr if 1, ethyl phenethyl, phenethyl, alkyl ketone such as acetyl ether, tilaquyl 1 silox such as pr nethylsiloxy, alkene such as 1-tp fluoro and ll-nitroethoxyethylene, such as silicone trirethylsilyl, alkyl tr alkylsilyloxybenzoic such as 2-tp? net ils? lox? rop-1-eml and Al coxi Ci-C, and L And R1 is H, CH3, CF3, (CH3) 3S ?, and CF3CH2-Z. The silylated organosilanes used in the According to the invention, cigars such as liquid or vapor, preferably steam, can be applied to a substrate. Organosilanes can also be used as solutions in solvents such as hydrocarbons and ether esters, and the solutions can be referred to as liquids or vapors to the substrate. Solvents of ; > Useful hydrocarbons include alkanes such as co or hexane, octane and the like, as well as aromatic solvents such as xylene, toluene and the like. Useful tert-esters include ethylene-1-methyl methyl acetate, propyl-methyl-1-methyl-methyl acetate, and the like. "Organosomes suitable for use in the invention include 0-t rimethyl silyl acetate (OTMSA), propionate 0 -t p me 1 is? 11 (OTMSP) 0-trirne-diisilyl butyl, tri-p-uoroacetate of tp-ethylsilyl (TMTFA), trirneti-lmethoxysilane (TMMS), N-rnethyl-N-tr-i and lsyl-lr-ri-o -acetacetate (MSTFA), crotonato de? net? l-3- (tpme ilsi iox), bi s (t rirnet ílsi 1 Ll) acetarni a, adipato de bisít r-? rnet? ls? 1 lio), bisitrene-1-ylsilyl) trifluoroacetarnide, 3- 5 tr *? Rnet? Ls? L? L-2-oxazoladinone, 1-thionyl-1-pyrrolidone, 0-t-alkyl-1-acetylacetylacetone (OTMAA), iopropenoxypropyl-lysilane ( TPTMS), b? S (t pnetilsi LLI) tp fluor * oacetam? a (BSñ), rneti acetate and tmethylsi lime dimethyl ice (MTDA) and t prnet letoxysilane (TMES). Other organosilanes that may be used include What is the opposite of 0-trunet i lsililo, 2-tpmet? Ls? Lox? These compounds are cornerally dispersible, and other compounds which may be used as the compounds selected in the invention include: L5 isopropenox t rimeti 1 silane and organosilyl sulfato s available from the formula: wherein R is C? -Ct alkyl, or fluoroalkyl Ci -C ?,.

Particularly suitable organosil isulfonates include tprnethyl if lilmetanosul fonto and 5 t ri net i 1 if ltp f 1 or romet il sulphonate. As mentioned, solutions of selected organosilanes in organic solvents can be used as silLladon agents. Suitable organic solvents that can be used with these organosi lanes include aliphatic hydrocarbons such as n-octane, hexane, and unary; aromatic hydrocarbons such as toluene, xi Log and the like; aliphatic ethers such as inetoxyl ether, diglyva and the like; and ether esters such as propylene glycol methyl ether acetate (PGMEA), ethylene glycol methyl ether acetate and the like. Solutions of the selected organosilines used in the invention can include one or more of the above-mentioned selected organs, with one or more organic solvents in a mixture of about 1:99 to 99: 1. A desirable solution includes OTMSA and PGMEA in an almost 1:99 to 99: 1 ratio of OTMSA to PGMEA, preferably almost 20:80 to OTMSA to PGMEA. The selected ilane bodies used in the invention can be applied to silylate a substrate before applying a photocurable substance to the substrate in a wide range of concentrations and proportions of mixtures dependent on the composition of the substrate, process temperatures, and equipment. Specific conditions for the application of the photoresisting substance can be determined by * those skilled in the art. Substrates that can be treated according to the invention include, but are not limited to sizing silicon wafers and silicon wafers which then have oxi or chemically or thermally generated surfaces. As used herein, it is understood that the silicon size wafers mean intact silicon wafers which are made directly from the manufacturer's shipment. Other sutures that can be treated according to the invention include chemical glasses such as borosilicate silicate glass (BPSG), metal layers such as aluminum, titanium, tungsten, copper and chromium, silicon dioxide, rnonoxide The silicon, chromium oxide, silicon oxide, aluminum oxide, titanium oxide, copper oxide, as well as various metal silicides such as aluminum silicide deposited on silicon oxide and titanium nitride. The sillation of a substrate by application Direct vapor from one or more of the selected lanos organs used in the invention can be carried out with commercially available steam sizing equipment. Examples of useful sizing equipment include Genesis Microstar 200, Genesis 2020 steam sizing unit, sizing unit steam Genesis 2010, steam sizing oven Genesis 2002, sizing equipment from Yield Engineepng Systems, Inc., in aligned steam tracking systems such as those manufactured by Silicon Valley Group, and supertrust tracking systems * 1íqui two. : -R Silylation by direct application of steam, as known in the art, is carried out by transporting a ") 'Z > mixing vapors from one or more of the selected organosilanes in gases such as nitrogen or argon within steam sizing equipment, or by flow of differential pressure vapors from the organosians in steam sizing equipment to the subsystem that is going < •• »make silos. The specific quantities of the selected organosilane compound used in steam can vary from almost 10 to 100,000 ppm, depending on the system, flow, time of exposure and vacuum used. Silylation by direct application of steam to the substrate can be carried out at temperatures of almost 10 ° C to almost 200 ° C, preferably almost 50 ° C to almost 150 ° C. Sililation according to the invention allows uniform organic films to be deposited on the silated surface of the substrate. Examples of films which can be deposited on the silylated surface include photo-recyclable substances, silicon poly nums such as those products produced by Arnoco Chemical Co. and Micro SI Tnc., Specifically ALTISTL 115, 129, 1000 and 2000, polyacrylates such as any of those mentioned above and including polymethylmethacrylate talus as commercial products produced by Amoco Chemical Co., Dupont Electronics, National Starch and Chemical Co., to name a few, novolac-based films such such as products produced by Micro SI Tnc., OCG Microelectromc Materials, Tnc, Shipley Co., Tnc, and planoplastic layers such as those produced by Fil troms, Futurrex, OCG Microelectronic Materials, Inc., and Dow Chemical Oo. The photocurable substances can be applied to the silted surfaces produced by the selected organosilines used in the invention by methods known in the art. These photocurable substances are typically chemically amplified high-resolution positive or negative-tone compositions which contain acyanurate and a photo-stabilizer. Useful photoresist substances include organic solutions of photoactivated polymers which contain photoinitiators. Useful photo-builders include orno salts or mixtures such as diaplyodome, arylalumonodomo, tparyl ufononium, sulfurylphosphonates, hexafluorophosphates je tpalqui 1 sulfonamide, hexaf 1-uoroarsenates, hexafluoroant monatos and tosylates, especially hexaf-1-uoroantunonate of 4-t-ofenox fem 1 difoni its fonium, di (4-ter-but ifem 1) iodonium hexafluorophosphate and hexafluor-oant-onate di-la-pl-4-t-but 1 fem Isul foruo; diazona ftenat os, such as diazoquinonosulonic acids or diazoquinonocarboxylic acids, especially 6-d? azo-3, 4-d? h acid? dro- -oxo-1-naphthene sulphonic; and azides, such as bi sary lazides, especially 2, b? s (4,4 diaz i dofeml-2, 21 etiieno) -4-rnet? lc? clohexanone. These photoinners are reactive to light between the wavelengths of 436 nin to 190 nm. Examples of useful photocurable substance compositions include, but are not limited to, those dif? Cultible from Shipley Co., Inc., Hoechst Celanese Corp. (AZ Photoproducts Division), Tokyo Oh to Chemical Co., Ltd., S 'hm-Etsu Chemical Co., Ltd., OCG Microelectromc Materials, Japan Synthetic Rubber Co., Ltd., TBM, Hitachi Ltd. and BASF Ltd. Specific photocurable substances include SNR200, SAL601, SAL603, XP-3115 and XP8844 from Shipley; Apex and IBM AST; OCG Carnp 5, BASF ST2; and AZPN114 from Hoechst, Ray-PN and PFR 1X750 from JSR. In an alternative embodiment, the photo-recyclable substance can be applied in combination with the organosilanes used in the invention. A mixture of photocurable material and at least one of the selected organosilanes used in the invention can be applied to the substrate. Typically, the mixture can be applied by mixing an organosilane selected from this invention with the photoresist material in an amount of 0.1 to 1.0% by weight of the solution of the photocurable substance, and applying the solution to the suspended substrates according to the manufacturer's instructions. of the photo-hardening substance. The photoresistible substances can be applied to a silylated substrate of the organosilanes used in the invention in a predefined pattem and then developed by known methods. Typically, these methods would enter the exposure of the photocurable substance to photons (including X-rays), ions or electrons of various wavelengths to form a film. The film is then chemically reacted with aqueous or organic developers. The present invention, wherein the selected organo compounds are employed as sililating agents, provides important advantages over the art. The selected organosiines do not generate undesirable basic by-products such as ammonia or dialqui lamies. Thus, the invention can provide * higher performance, more CD control, elimination of the need to apply additional barrier coatings to protect the photoresist, reduced silage times, as well as longer braiding times to reduce the load deposited on systems of air purification. The invention also makes it possible to control the surface silification of the wafers at speeds higher than those of HMDS, but without generating undesirable basic by-products such as ammonia. The effectiveness of the selection of the selected organosilanes used in the invention in the form of liquid and vapor is given in Tables I and II, respectively. Other illustrations are given in examples 1 to 23. The effectiveness of sizing is determined by mulling the contact angles with an Arthur H. Thomas goniometer available from flrthur H. Thomas Co. using the procedure reported in NISTLER and in MOREAU mentioned above. The measurement of the contact angle is given by A. U. Adarnson, Physical Chernistry of Surfaces, 4th ed., Wiley Tnterscience, NY, 1982. Greater contact angles denote higher degrees of separation, ie, effectiveness of sizing. However, contact angles greater than 85 ° indicate excessive sizing, which can lead to adhesion losses of the photocurable substance and blistering during exposure to chemical developers. None of the selected organosilanes used in the invention generates contact angles greater than 85 ° under the conditions used. 1. Contact angles determined in Arthur H. Thomas goniometer. 2. FAST HMDS ™, available from Silicon Resources, Tnc, contains a mixture of DEATS and HMDS. 3. Silicon dioxide (thermal) 4. estimated contact angle, since contact angles less than 15 ° are difficult to measure.

Each of the substrates in Table I is prepared under the following identical conditions on sizing wafers of 100 nm diameter, three wafers per operation: The sizing is carried out by treating a stationary wafer in a 10 second bath of the liquid silylating agent. The wafer is then stirred at 2000 rpm for 30 seconds. In the operations shown in Table TT, the steam sizing with organosines according to the invention is carried out in a Genesis 2020 steam sizing unit adapted with a Hot BIOC ™ TM adapter from Genesis Co., using the same periods and temperatures given in the ET box 1. Sizing silicon wafer 100 rn. 2. Silicon dioxide developed thermally on 100 mrn silicon wafers. 3. The contact angle is estimated because the angle of action less than 15 ° is difficult to measure. 4. No silicon uro purified in plasma O2 before sizing. 5. Pol i l licio. 6. Glass of boron phosphorus silicon. The measurements of the contact angle of the pictures T and II show that the degree of silylation achieved by the organosilanes used in the invention, whether in the form of liquid or vapor, is equal to, or greater than, that achieved by HMDS. The invention has special utility for manufacturing romeos and semiconductor semiconductor devices. However, the invention can be used in any process that requires the adhesion of a polymeca film such as a water-resistant substance to a substrate surface. Examples of these methods include preparation of photon-scavengers on any glass substratum or any, circuit boards, thin film heads, sensors, TF sensors and liquid crystal exposures of active r * z z. However, the invention can promote the sil ilation of a variety of substrates suitable for the coating of photo-recyclable substances in equipment. existing with little or no modification. The invention will now be described in detail in relation to the < siguient.es specific non-limiting examples: EXAMPLES 1-3 A series of 5 commercial silicon sizing wafers of 100 nm from SEH Co. is treated with HMDS of liquid semiconductor grade on a coating system model No. 8600 of SVG Lithography Systems, Inc. ("SVG") under The following Lenses conditions: A stationary wafer is given a 10-second bath of undiluted liquid HMDS available from Silicon Resources, Inc. under the key of Product AP010. The wafer is rotated * then at 500 rpm for 2 seconds, and then stirred at 2000 rpm for 30 seconds. A baking stage is not used. A series of 5 commercial 100-m sizing wafers from the same manufacturing batch is treated with undiluted OTMSA liquid (98% purity) under these same conditions. For comparative purposes, a series of 5 silicon sizing wafers of 100 rnm untreated is evolved. Readings on a goniometer using an Arthur H. Thornas Co. goniometer are made on each wafer using the procedure described above, the contact angles are measured and averaged. The results are given in table III: 12 TABLE III EXAMPLE No. AÍTE DE SI SI ILACION FOLLOW OF CONTACT HMDS 44 'OTMSA 50' None 34 ' EXAMPLES 4-6 A series of 5 commercial silicon sizing wafers 100 ml from SEH Co. is treated with a 20% (w / w) HMDS solution in PGMEA in the SVG tracking system used in examples 1 to 3 A second group of 5 100 mrn sizing wafers is treated with a 20% OTMSA (w / w) solution in PGMEA in the tracking system. Each wafer is treated under the following conditions: Each wafer is given a bath of ten seconds of solution followed by rotation for two seconds at 500 rprn and then stirring at 2000 r p for ten seconds. This is followed by baking at 100 ° C for 15 seconds. The results of the measurements of the contact angle in the goniometer using the procedure described above are given in Table IV: '13 TABLE IV The greater contact angle observed for the OTMSA solution compared to the HMDS solution indicates a more efficient sil ilation with OTMSA.

EXAMPLES 7-8 A series of three silicon sizing wafers of 100 nrn is treated with MSTFA (N-ethyl t rirnetilsi Ultp-fluoroacetarruda-grade chromatography, 98%) in the SVG tracking system used in example 1, submitting to the wafers to a steam bath for 10 seconds followed by rotation «for 2 seconds at 500 rpm and then stirring at 2000 rpm for 30 seconds. Each wafer is then baked for 30 seconds at 100 ° C. An identical number of wafers is steam treated from HMDS from HMDS available from Silicon Resources, Inc. under the APOLO product key under identical conditions. The measurements of the contact angle taken with a goniometer as described above are shown in Table V: TABLE V The dampening wetted indicating strips located in the discharge of the rotation cup of the SVG tracking system most r * o that the discharge vapors due to the use of HMDS had a pH of 10-11 for HMDS and a pH of 7 for MSTFA.

EXAMPLES 9-11 A series of silicon and sizing wafers are treated with HMDS steam from pure HMDS available from Silicon Resources, Inc. under product code AP 10. The steam treatment process involves placing the wafers in a sizing unit. Rum vapor G nesis 2020 of 200 torr as measured nedian + e a vacuum meter of convection type. The unit's dehydration firing cycle is not used. The silage of the wafers for 60 seconds begins when the temperature equilibrium of 50 ° C is achieved inside the chamber of the steam unit. A second series of sizing silicon is treated with OTMSA vapor (reagent grade, <J8% purity) or identical conditions and a third series is treated with steam of -J! Rr > TMSDEA available from Silicon Resources, Tnc., Ba or product code fiPOOl ba or identical conditions. A goniometer is used as described above to measure * the contact angles of the wafers treated after the second exposure to steam. The results are shown in table VI: TABLE VI 0 EXAMPLES 12-14 Reactive grade OTMSA vapor, 98% pure, is used to treat silicon wafers having a silicon nitride surface on them. Wafers are available from Si lica Source Technologies Corp., Tempe AZ. The contact angles of the nitrided wafers are measured. The contact angles of the wafers after the treatment with ) f) OTMSA steam at 50 ° O for 10 seconds, and the wafers after steam treatment * of OTMSA at 50 ° C for 30 seconds are also measured, the contact angles are measured using a goniometer as described before. The results are shown 3fi in Table VII: TABLE VII 1.- Angle of contact estimated from angles less than 15 'are difficult to measure. 2.- Treatment at 50 ° C for 10 seconds. 3.- Treatment at 50 ° C for 30 seconds.

EXAMPLES 15-17 A silicon wafer < : * that it has a surface of silicon dioxide on it obtained from Silica Source Technologies Corp., and that it has a measured contact angle H * less than 15 °, as determined with a goniometer as described above, is treated with steam from the OXJ < pmet lsilane (TPTMS) from reagent grade IPTMS, 98% purity, at a temperature of L00 ° C for 30 seconds in the Genesis 2020 steam sizing unit used :) 0 in example 9. The identical treatment conditions were also used to treat an identical wafer with HMDS vapor. The contact angles measured with a gomornet.ro as 1 7 described earlier are given in Table HIV: TABLE VIII 1. - Estimated contact angle from angles less than 15"are difficult to measure.

EXAMPLES 18-19 Silicon sizing wafers from SEH Co., previously treated with OTMSA steam (reactive grade, 98% purity) in a Genesis 2020 steam sizing unit equipped with a * Genesis HOllLOCKTM adapter for 60 seconds at 100 ° C and was found by measurement with the goniomene or as described above having an angle of contact in an average of 72", they are coated by rotation with Shipley Oo. SNR-200, and baked slightly at 125 ° C for 60 seconds To produce a film thickness of 1 miera, it is observed visually that the photocurable film does not present edge curl.The film is exposed to 248 nm on a stepper * GCA XI -2950 «je 0.50 na, (40MJ / crn2) with a post-exposure at 130 ° 0"for 60 seconds through a masker having an objective line width of 0.50 μn.The product is indicated by Shipley Co. MFR CD-14. I indicate line pairs / space of 0.48u? n for HMDS and the wafers to which OTMSA was applied as sizing. The results are given in Table IX: TABLE IX eleven The results indicate that it is equal or better in performance than HMÜS and does not change and interfere with the yield of the photocurable product and < ] That OTMSA can be used * interchangeably with HMDS without adverse effects. ? > \ EXAMPLES 20-22 A series of 100-nm silicon wafers coated with a 1-mm thick aluminum layer obtained from Silica Source Technologies Corp., Tempe, A7 is treated with HMDS 0 available from SLlicon Resources Inc., under product code AP010? 100 ° C for 30 seconds in a Genesis 2020 steam sizing unit equipped with a HQTBLOCKTM adapter.

Using identical conditions, a series of two of the same wafers is treated with steam * from OTMSA derived from the liquid OTMSA (98%, Upght Chemical 00.), and a *, epe of "those from the same wafers is tied with TPTMS vapor obtained from liquid TPTMS (97% purity). The results of the contact angle measurements with the goniometer < That they use the procedure described above are given in Table X: TABLE X 10 EXAMPLE 23 A silicon sizing wafer of 100 rnl having a "contact angle measured with 32 ° goniometer according to '.r-f-, I determine using the above procedure is treated with steam-TMTFA derivative Liquid TMTFA (97% «purity) in the Genesis 2020 steam sizing unit employed in example 20 for 15 seconds at 50 ° C. The contact angle as measured by a goniometer as described above indicated a contact angle of 71 °. The experts in the art will appreciate that changes can be made to the modalities described above without departing from the broad inventive concept of the same Cars, therefore, it is understood that this invention is not limited to the particular embodiments described, but < It is intended to open such modifications within the spirit and scope of the present invention as defined in the appended claims.

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - An improved method for providing a silylated substrate having improved adhesion to polyrneric materials which comprises reacting at least one organosilane compound having at least one alkylsilyl moiety thereon with a substrate ba or sufficient conditions for sillar * substrate, said alkylsilyl portion having at least one hydrolysable residual group attached to the silicon, wherein said hydrolysable group is capable of reacting with the substrate to generate by-products having a pH less than or equal to 7"

2. - The method according to claim 1, further characterized in that the substrate is selected from the group consisting of at least silicon "individual crystal, polysilieio, silicon dioxide, silicon mt uro, aluminum, aluminum oxide, copper , cobr-e oxide, titanium, titanium-titanium-tungsten, borosorphite, glass «boron-phosphorus-silicon, rotating glass, metal oxides and silos ci uros

3 . - The method according to claim 1, further characterized in that said polyphenolic material is a photopenic substance which comprises a polymer selected from polyvinylphenol, polyhydroxymerone,? ) -It is reno, pol i smoking, poly (t-butoxiest i reno), polyoprenols, novolacs fo fo due, and polyacrylic esters.

4. The method according to claim 3, further characterized in that the photocurable material includes a cyanurate and a photoinitiator selected from the group consisting of oval, diazonafen and azide salts.

5. The method according to claim 1, further arranged because the organosilane is a tpalkyl silane.

6. The method according to claim 5, further characterized in that the tnalkylsilane compound has the formula: CH3 Y | || H3C - S1-X-C-R I CH3 on «where X is O, or NR *; Y is 0, CH2, CHR, CHOR, CRR or NRi; R is hydrogen, saturated Ci-C alkyl, saturated cyclic alkyl from 04-06, saturated Ci-C alkyl, unsaturated cyclic alkyl from Ct, -Ce; fluorinated cyclic alkyl of Cs -Ce, trialkylsiloxy, t ñaiqui lsil 1 lo, C1-C12 alkoxy, phenyl, fluorofemlo, phenetiio, or alkylethoxanes of O3-Ce; and R1 is hydrogen, methyl, tritluoromethyl, tp f 1 or rornet 1 let 1 lo, or tprnetiisi lilo.

7. - The method according to claim 6, further characterized in that the t palquilsi loxi is (CH3) 3? 0, the t palquilsi lilo is (M 3) 3? , and the fluorofemlo is Cßl-UF. The method of conformity with claim 1, further characterized because the organosilane compound has the formula: CH3 H3C-S1-OR2 I OH3 wherein R is saturated C 1 -Ce alkyl, C 3 -C 8 saturated cyclic alkyl, C 2 -Ce unsaturated alkyl, Ct unsaturated cyclic alkyl, -Ce, Ci -Ca fluorinated alkyl, Cs -Ce fluorinated cyclic alkyl, fem lo, fem fluorinated, C3-C6 alkyl ketones, C2-C9 alkyl ether, unsaturated alkyl ketone of C3-Ce, fluorinated alkyl ether. 9. The method according to claim 7, further characterized in that said fluorinated femlo is Csl-UF and said ether at < Fluorinated juicer is f 1 uoroalcoxyether of C3 -Ce. 10.- The method in accordance with the rei indication 9, further characterized in that the saturated alkyl is saturated f 1 uoroalkyl. 11. A method according to claim 1. 10, further characterized because the fluoroal uilo saturated is t ri f 1 uo romet 11 o. 12. The method according to claim 1, further characterized in that the organosilane has the formula: in which R3 is straight or branched chain saturated alkyl. 13. The method according to claim 1, further characterized in that the hydrolyzable group is selected from the group consisting of acetates, carboxylates, enols, alkoxides, sulphates and amulas. 14. The method according to claim 5, further characterized in that the tialkyl silane compound is 0-tpmet acetate 1 ls? li lo. 15.- The method according to the claim 5, further characterized in that the tpalquilsi-lano compound is iopropenoxytirnetyl ilsilane. 16. The method according to claim 5, further characterized in that the compound of t ñaiqui 1 silano is N-rnetiltrirnet 1 isyl ilf p fluoroacet aní da. 17. The method according to claim 5, further characterized in that the tnalkylsiline compound is t-methyl-methoxysilane. 1

8. The method according to claim 5, further characterized in that the t-palkyl silane compound is tmethylethisilane. 1

9. The method according to claim 1, further characterized in that the organosilane compound is reacted as a vapor with said substrate at temperatures from room temperature to approximately 121. 1 ° C and pressures from about atmospheric pressure to about 1 torr *. 20.- The method "Je conformity with the claim 1, further characterized in that said organosilane is an alkylaryl Isilane having two reactive hydrolysable groups attached to the silicon. 21. The method according to claim 20, further characterized in that said dialkylene is selected from the group consisting of dimethyl-irnetoxysilane and d-ir-11di-acetoxy if the o. 22. A method for providing a photoresistible film on a substrate comprising providing a composition providing a composition comprising a compound "organosil no" has at least one alkylsilyl portion and a photocurable material, said portion alkylsilyl having at least one alkylsilyl portion and a photocurable material, said alkylsilyl portion having at least one hydrolyzable group attached to the silicon, and applying said composition to a substrate to silate said substrate and to produce a film of said material. ? reci ble on said substrate, wherein said hydrolysable group is capable of reacting with the substrate to generate byproducts having a lower pH < ? ue or equal to 1. 23. The method according to claim 22, further characterized in that said substrate is selected from the group consisting of at least << ie individual glass silicon, polysilicon, silicon dioxide, silicon dioxide, aluminum, aluminum oxide, copper, copper oxide, titanium, titanium truro, titanium-tungsten, boron-phosphorus, boron-phosphorus-silicon glass , rotatable glass, metal oxides and chloride. 24. The method according to claim 22, further characterized in that the compound "organosilane is a dialkyl is having two reactive hydrolyzable groups attached to the silicon. 25. The method according to claim 24, further characterized in that the dialkylsilylene compound is selected from the group consisting of d-dimethylethoxysilane and dimethylacetoxy silyne. 26.- A method for providing a silylated substrate having improved adhesion for poly-epic materials comprising reacting at least one organosilane compound selected from the group consisting of o ~ trirnetii silyl (OTMSA), o-tpmethylsilyl propionate (OTMSP) ) o-tr? met? itol butyrate, tpf luor-oaceta or tprnethylsilyl (TMrFA), trirnetumethoxysilane (TMMS), N-me + ni-Nt rirnet. l-s? l? ltp fuoroacetarnide (MSTFA), 0-tprnethylsilacetiiacetona (OTMAA), lsopropenoxitprnet lsiiano (EPTMS), b? s (tr? nel ílsil i 1) tp f luoroacetarní da (BSA), rnetiltrimet ls acetate? lylimethoxy ketone (MTDA) and tyrrene-letoxysilane (TMES), with a substrate or under conditions sufficient to remove said substrate, said organosilane having at least one hydrolyzable group attached to the silicon, said hydrolysable group being capable to react with the substrate to generate byproducts < which have a pH less than or equal to 7. 27.- The method according to claim 26, further characterized in that said substrate is selected from the group consisting of individual crystal silicon., silicon dioxide, silicon dioxide, silicon nitride, aluminum, aluminum oxide, copper, copper oxide, titanium, titanium nitride, titanium-tungsten, boron-phosphorus, boron-phosphorus-silicon glass, glass gi , oxides of metals and silicides. 28.- A clamped substrate produced by the method of claim 25. 29. The substrate of claim 28 further characterized in that it comprises a poluneric coating on the same. 30.- The substrate of claim 29, further characterized in that said polimeric coating is a photocurable substance. 31.- A method to produce a subs rtat? coated, which comprises reacting at least one organosilane compound having at least one alkidyl portion therein with a substrate ba or conditions sufficient to remove said substrate, said alkylsilyl portion having at least one a group hydrolyzes ie attached to the silicon, wherein said hydrocyanatable group is capable of reacting with the substrate to generate by-products having a pH less than * or equal to 7 and applying a polyrneric material to the substrate treated with said agent if provide coated substrate. 32.- The method of compliance with the claim 31, further characterized in that said substrate is selected from the group consisting of at least individual crystal silicon, polysilicon, silicon dioxide, silicon oxide, aluminum, aluminum oxide, copper, copper oxide, titanium, nitr? titanium-titanium-tungsten, boron-phosphorus, boron-phosphorus-silicon glass, rotatable glass, metal oxides and silicones. 33.- The method of compliance with the claim 32, further characterized in that said polymeric material is a photocurable material comprising a compound selected from the group consisting of polyvinyl phenol, polyhydroxy ester, poly (t-butylcarboxy) -ste reindeer, poly fumarate-cough, poly. (t-butox? est? reno), polusoprenes, formaldehyde novolacs, and pollacrylic esters. 34.- The method of compliance with the claim 33, further characterized in that the substrate has an adhesion for the photocurable substance which is at least as large as l e. adhesion generated by HDMS for the photohardenable substance.