TW200807705A - Semiconductor optoelectronics devices - Google Patents

Abstract

A semiconductor device comprising a semiconductor substrate with a plurality of photo-diodes arranged in the semiconductor substrate with interconnect layers defining apertures at the photo-diodes and a first polymer which fills the gaps such as to cover the photo-diodes. Further, layers of color filters are arranged on top the gap filling polymer layer opposite to the photo-diodes and a second polymer arranged on the interconnect layers covers and planarizes and passivates the color filter layers. On top of the planarizing polymer there is a plurality of micro-lenses opposite to the color filters, and a third polymer layer is deposited on the micro-lenses for passivating the micro-lenses. According to the invention the polymer materials are comprised of a siloxane polymer which gives thermally and mechanically stable, high index of refraction, dense dielectric films exhibiting high-cracking threshold, low pore volume and pore size.

Description

200807705 24699pif IX. OBJECTS OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to a process for fabricating a semiconductor device by using a novel polymer. In detail, the present invention provides a novel semiconductor in which polymerization of a functionalized monocyte is utilized. The compound is combined to form a complementary meta-oxide semiconductor (compoundary metai oxide semic〇nduct〇r, CM〇s) with less image sensing or optical layer or electric layer. Further, the present invention focuses on integrated circuits

And optoelectronic devices and methods for treating new polymeric materials at the time of manufacture. [Prior Art] The commercial use of electronic image sensors in electronic technology has been increasing in recent years. Electronic image sensors can be found in cameras, cell phones, and in new safety devices for vehicles (for example, to estimate the distance between vehicles, to accumulate blind spots that are not exposed by mirrors, etc.). Many semiconductor manufacturers convert their production lines to CMOS sensor production to meet this need. CM〇s inductors use uranium for many processes in the manufacture of standard integrated circuits (1C) and do not require large capital investments to produce devices of the current state of the art. In the bottom-up process, the photodiode (phot odiode) is built in the stone layer. Standard dielectric and metal circuits are placed on the diode to transfer current. The optically transparent material disposed directly on the diode is optically transparent (4) that transfers the surface of the device and passes through the color filter (10)-fiI (four) to the photodiode. Transparent slabs and flattening materials are usually placed on the color filter w and on the device. The microlens is placed on a flattened film layer on the ^ 6 200807705 24699pif color filter to improve device performance. Finally, the protective layer may be placed on the lens or the glass slide may be placed over the lens array, leaving an air gap between the lens and the cover. Most of the CMOS inductors are constructed using one or more layers of metallization using a subtractive/chemical vapor deposition (CVD) oxide metallization. For the production of a planarized film layer or microlens, an organic polymer such as a polyimide or a novolac material is also used, or a siloxane polymer may sometimes be used. Organic polymers can be divided into two different groups according to their dielectric constants (didectric coffees). Non-polar polymers contain molecules with almost completely covalent bonds. Due to non-polar polymers, they are mainly composed of non-polar c_c bonds. Therefore, the dielectric constant can be estimated using only the density and the chemical composition. The polar polymer does not have low loss, but it contains atoms of different electronegativity, resulting in an asymmetric charge distribution. Therefore, the polar polymer has a higher dielectric Electric mussel consumption and dielectric constant, depending on the frequency and temperature at which time is evaluated. Several organic polymerizations have been developed for the purpose of dielectric properties = 2 However, due to the low thermal stability of these layers (thermalstaWlityf , softness (s〇ftness) and incompatibility with the development of conventional technology processes based on Si〇2 dielectric, the above-mentioned film layers may be limited. For example, organic polymers cannot Chemical mechanical polishing (CMp) or dry back: etching without damaging the film. The recent focus has been focused on sesquioxane-based Xiyuan or Shixi oxygen 200807705 24699pif burnt (four) sesqmoxane or siloxane, SSQ) or dioxide dioxide and light materials. For SS (3 material, sesquioxide # = burn) as the basic unit. sesquioxalate Burning or tau resin (T_resin) = two-test (4) 〇 3/2) n organic/inorganic hybrid polymer. These materials are represented by a ladder-like structure, and the cage structure containing the eight H sub (τ8 cube) placed on the apex of the cube can be wrapped, and the organic substitution of nr and its "Si" has the common organic k has good Loose resolution. Organic substitutes provide low density and low

Constant matrix material. The lower dielectric constant of the matrix material is also attributed to Si〇2 t ^ Si.〇tb Si.R , and the material based on the seso-oxygen frequency in the microelectronics is finally hydrogen_silsesquioxane5 HSQ and _ sesquioxane (methyl_silseSqUi〇xane, material has a lower dielectric constant compared to the larger size of the CH3 group, which is about 2.8 and lower, respectively, and Si- compared with Si_H The lower polarization of the CH3 bond. However, the refractive index of these layers in the visible range is usually between about Μ and L5, and is usually less than 16. The material based on vermiculite iridium oxide has Si 〇 2 Tetrahedral basic structure. Vermiculite ceria has a molecular structure in which each Si atom is bonded to a molecular structure of four oxygen atoms. Each helium atom is in the middle of the tetrahedron of the oxygen atom, that is, it forms a bridge. Bridging crosslink. All pure vermiculite ceria has a dense structure with high chemical stability and excellent thermal stability. For example, amorphous vermiculite used in microelectronics technology 200807705 24699pif

The cerium oxide film has a density of 2.1 g/cm 3 to 2·2 g/cm 3 . However, due to the high frequency dispersion of the dielectric constant associated with the 咼 polarization of the Si-Ο bond, the dielectric constant is also high, ranging from 4·〇 to 4.2. Therefore, it is necessary to replace one or more Si-OSi bridging groups with a C-containing organic group (such as a ch3 group) which lowers the k value. However, due to sterjc hindrance, these organic units reduce the degree of bridging crosslink and increase the free volume between molecules. Therefore, the mechanical strength (Young's modulus < 6 GPa) and the chemical resistance are reduced as compared with the tetrahedral ceria. Again, such methyl-based silicates and SSQ (i.e., MSQ) polymers have relatively low rupture thresholds, typically about 1 μηη or less. SUMMARY OF THE INVENTION One object of the present invention is to provide a novel high refractive index cerebral oxygen polymer (siloxane p〇lymer) which is compatible with conventional integrated circuit (IC) and CMC)S. ). The goal is to provide a modified (mc) dify) monomer (_.黯) to the side; f-type organofunctionalized molecules (.rga, functionalized molecule) of the first ', Le two to provide the production of poly (organic stone) Xiyang:: The composition is suitable for the preparation of a polymer having excellent dielectric properties to form =. (3) The fifth objective of the present invention mentioned above is to provide a dielectric layer to Shi Xi and Glass wafers 200207705 24699pif This known dielectric, as readily apparent from the following description, and the invention for its preparation =_= target, together with its preferred embodiment, are completed. The advantages of the method are described below. ^成二等: standard, the introduction of a new polyorganic semiconductor or optoelectronic device shirt and as a phase insulating film for semi-straight monomers comprising: at least two metal atoms, the United States · light on the metal atom shows hydrolyzable substitution The 2222 organic group's ability to reduce the polarizability of the polymer 'widely' "not to form a nanometer-sized porosity (ροκ>ϋ) in the polymer or all (four) characteristics of the monomer shape Combination. The 'metal atom is an atom, and the bridge The base is a linear shirt (four) or / knife branch (b (four) (divalent) smoke base to bond two stone atoms together. In addition, usually (four) - contain three hydrolyzable groups, and another - Shi Xi atom contains a water-based _ and _ turnover group, reactive cleavage group or polarized reduced organic group (such as alkyl, alkenyl, alkynyl, aryl, polycyclic group or Containing an organic containing silicon group. The latter group may also be fully or partially fluorinated. Formula I used in the present invention is of the formula: 200807705 24699pif wherein: R] Is a hydrolyzable group (such as hydrogen, halide, alkoxy or acyloxy group); & is hydrogen, organic crosslinking group, reactive cleavage group or polarized reduced organic group And < is a bridged or branched divalent hydrocarbon group. In the method of the present invention, Formula I covers two slightly different types of precursors, i.e., corresponding to the first primary precursor of Formula I, the center of which represents hydrogen The second type of precursor has the formula j, wherein & represents an organic crosslinking group, a reactive cleavage group or a pole Reducing the organic group or a combination thereof. These groups are represented by an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a polycyclic group, and a group containing a oxime. The group according to the & The compound can be formed by a hydrosilylation reaction in which trihalosilane and dihalosilane are reacted in the presence of a cobalt octacarbonyl to form a good The intermediate of 1,1,1,4,4-pentafluoro-1,4-pentahalol (4-disilabutane) was produced. This intermediate can be converted, for example, by hydrogenation of hydrazine to replace the hydrogen at position I to form an organofunctional decane. If the R2 group is a reactive group, the group can decompose during the film layer curing process and leave a crosslinking group or a polarizing reducing group or combination. The polymer of the present invention is obtained by hydrolyzing a hydrolyzable group of a polydecane monomer or a combination of the polymers described in the present invention or a molecule of the present invention in combination with a technique of the above-mentioned technology in the art of 200807705 24699 pif 1 and then by condensation polymerization. The process proceeds to the step of polymerizing it to produce a film. For example, it can be used as an optical interface in articles containing (cut) wafers. 5 inventions are also provided - formed to have a thickness of 4.G or less (or Good dielectric constant and greater than 632.8 wavelength range

V.., a method of film having a refractive index of (10), comprising: forming a stone oxide composition of the material, forming a stone oxide composition in a thin layer, and solidifying the germanium layer to form a film layer . A number of advantages are obtained from current novel materials and by methods of making them. ^ This, the present invention proposes a solution to the problem with optical polymers. More specifically, the present invention proposes a solution to the existing problems of refractive index, (10) capacitiveness, mechanical miscellaneous (abbreviation and hardness), breaking and limiting characteristics, "test 1C integrated body temperature. In particular, the ruthenium film layer is also suitable for light or foreseeing (preferably ultraviolet (iv) raviolet, uv) wavelengths or electron beams (e_beam^ enhanced curing) as needed during the thermal curing process. New organofunctional molecules can be built to be able to This form of further reaction in the matrix. This means that the organic function of the molecule can, for example, undergo cross-linking, splitting, or a combination of the two (ie, subsequent splitting and cross-linking) The South Father's Union has excellent density and excellent chemical resistance and very low chemosorption properties. If the R2 group is a split group, it still results in a very small pore size (ie 'normal h5 nm or Smaller. However, the polymer formed according to the invention is also compatible with a conventional type of porogen such as cyclodextrin (Cycl® (Jex Duin), which is formed according to the innovation 200807705 24699pif. The agent can be used to form micropores in the polymer and thus reduce the dielectric constant of the polymer. Another important advantage is that the novel optical dielectric materials have excellent localities in the configuration of the semiconductor substrate. And the excellent planarization characteristics of the global flatness, which reduces or even completely eliminates the need for chemical mechanical planarization after dielectric and oxide deposition. In addition, the new material has excellent gap fill characteristics. The particle is incorporated into a refractive index (about 175 or even ▲ ▲ ▲ ▲ ▲ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The refractive index that is incorporated into the intercropping circle makes the new material particularly suitable for CMOS cameras. U Kezhen is used to provide an optical mediator, and the pot is suitable for crucible rupture. Weekly heat stable and machine Haohua ~ (4) (4) and the pore size after the heat treatment will be the lit rate _ dielectric film. The polymer is subjected to gap filling non-water and no Shi Xiyuan alcohol (10) = king, thousand degrees and characteristics and Optical tec., S, which has excellent electrical properties at the final curing temperature, and the film layer made of the composite is subjected to high electrical and electrical properties; after final curing, its structure and mechanical properties are dielectric polymers. Overcome The characteristics are superior to the conventional optical pre-conductor + conductor device to improve the performance of the device as the key white t-version 200807705 24699pif Next, the present invention will be examined more precisely by means of the following embodiments and with reference to many works. The invention provides a county-level dielectric polymer comprising at least one more than one stone-stone monomer unit of a stone-free one organic bridging group, and another A-stone eve-f- of the group also contains an organic A group, a reactive splitter, has a combination of just-reported species (such as an alkyl group, an alkenyl group, a polycyclic group, or a zeolitic group). Hydrolyzable groups, and the other contains two consecutive stones / gas, the group - once hydrolyzed and polymerized, can form the money but the most chain f 'such as hydrogen, halide, alkoxy or acidoxy , terracotta, cerium oxide or ethoxylate groups or any combination thereof. The general formula I used for the pre-polymerization of the present invention is as follows:

In the hair, is a hydrolyzable group; a mechanical base 2 or an organic crosslinking group, a reactive cleavage group, a reduced polarizing group, and a combination of all of the foregoing, such as an alkyl group, an alkenyl group, an alkyne a aryl group or a aryl group containing a fluorene group; and c is a linear or branched divalent hydrocarbon group. I is a group selected from the group consisting of a compound, an alkoxy group, an alkoxy group, and a hydrogen group of 200807705 24699 pif, and I is preferably selected from an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, a polycyclic group or an organic group. The group, and & is preferably selected from the group consisting of linear and branched alkylen: aikenylene groups and alkynylene groups, j and a 'bivalent alicyclic group' (polycyclic group) And a divalent aromatic aryl group, which are all included in the definition of a divalent hydrocarbon group. • consisting of a monomer that substantially homopolymerizes the above formula, which is subsequently cured to achieve a cross-linking composition comprising a crosslinked organic $oxygenated polymer, that is, a poly(organosiloxane), which can be formed into film. "Alkenyl, as used herein, includes both straight-chain and branched alkenyl groups (such as ethenyl and propenyl). The term "alkynyl" as used herein includes both straight-chain and branched alkynyl groups (suitably Acetylene). "Aryl," means a substituted or unsubstituted mono- and bi-family cyclic carbocyclic group; the aryl group is phenyl, naphthyl or pentafluorophenyl propyl. As used herein, "polycyclic," includes adamantyl trimethyl dimethyl adamantly ProPyl, norb rnyl or g^norbornene. More specifically, the alkyl, alkenyl or alkynyl group may be linear or branched. The alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to carbon atoms, and particularly preferably contains fluorene to 12 carbon atoms. The alkyl group preferably branches at a position of . or oxime, having one or more (preferably two) Ci to Q alkyl groups, especially preferably halogenated (in detail, partially or fully fluorinated or perfluorinated) Per-fluorinated) an alkyl, alkenyl or alkynyl group. Some examples are non-fluorinated, partially fluorinated and perfluorinated isopropyl, tert-butyl, butyl-2, fluorenylmethylbutyryl and 1,2-dimethylbutan-2-yl. In particular, the base is a lower alkyl containing the 200807705 24699pif anatomical atom, which is optionally selected and one to three substituents of the dentate. Methyl, ethyl, n-propyl:, a base, an isobutyl group and a third group are particularly preferred. The base preferably contains 2 to 18 carbon atoms, more preferably 2 to 14 stone counters, and particularly preferably 2 to 12 carbon atoms. The group of ethylene (i.e., the two carbon atoms bonded by a double bond) is preferably located at position 2 or more, and the S atom of the octave is related. Preferably, the branch county has one or more (preferably two) Cl to C6 alkyl groups, an ene group, particularly preferably a fluorinated or perfluorinated base group, and a base group at the α or β position 2. Or alkynyl. The alkynyl group preferably has 3 to 18 carbon atoms, more preferably 3 to 14 stone atoms, and particularly preferably 3 to 12 carbon atoms. The group of the ethyl group (i.e., the two carbon atoms bonded by a double bond) is preferably related to the Si atom in the position molecule. The branched alkynyl group preferably has one or more (preferably two fluorene- to-alkyl, olefin or alkynyl groups, particularly preferably a perfluorinated, olefinic or alkyl group. The ring group may be a polycyclic aliphatic group including a wire which is caught by a ring-shaped knot having 5 to 2 carbon atoms, such as a ^ ^ ^ ( , tJ ^ (ada^ntylene) 〇 ^ (a coffee e)" represents a divalent aryl group containing up to 6 rings (preferably! to 6 fused rings (4) 2 3 and = 2 to 5 fused rings) (such as phenyl, thiophene and anthracene) (ant}iracenyl;)) The aryl group is preferably a phenyl group which optionally has a dentate or an alkane substituent selected from the ring; or a zeoliyl group which optionally has a halogen-based structure on the ring structure. i, n substituents of silk, silk or gynecyl, replacing 200807705 24699pif base as needed for reduction (including perfluorination or partial fluorination). Example: for golden duck, dimethyl fund base propyl, lower generation Depending on the need, «_ . . . . ^ " The olefinic, alkynyl or aryl group is separated from the ruthenium atom. t such as: bis? ? Table 11 (chloro, fluoro, bromo), alkoxy (detailed), °" ethoxy, propoxy or butoxy CM Alkoxy

iL: 'Easily, during the polymerization (e.g., condensation polymerization), any other groups of the monomer are opened. The 2 group generally represents a group having the formula R4〇, wherein R4 is as defined above: 疋= group: The alkoxy group-based residue may be linear or branched. The oxonite contains a lower alkoxy group having 1 to 6 carbon atoms (such as a thiol group, an ethoxy group, and a third butoxy group).醯^,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, $ or I atom and preferably F or a. Generally, the terminology herein refers to a fluorine, gas, bromine or iodine atom. In the monomer of formula I, the ruthenium atoms are bonded to each other via a linker group (Iinker group). Typically, the linking agent comprises from one (preferably from about 1 to about 10) carbon atoms. Examples of suitable linking group & alkylene, alkenylene and alkynylene. "Alkylene," generally has the formula (CHfr 'where r is an integer from 1 to 。. One or both of the hydrogen of at least one unit -CH2- may be replaced by any of the substituents mentioned below : 200807705 24699pif In the case of at least one triple bond group = at the alkylene residue 'which contains a number of double bonds in the hydrocarbon backbone, which is difficult to co-exist. The group contains a divalent bond of a primary bond corresponding to a sub-alkyl residue to be an unsubstituted slit. The substituent is preferably selected from the group consisting of an oxy group, a secret group, a Q group, a thiol group, a Ci_iq group, and a c(tetra)aryl group. , acryl, epoxy, hetero, and group of counties. Particularly interesting (iv) substitutes contain a methylene group substituted with at least a silk (preferably lower filament or hydrazine to 4 carbon atoms). As a result of the substitution, a branch is obtained. a linker chain. A branching linker chain (eg, '-CH(CH3)-) can have as many carbon atoms as the corresponding linear (eg, -CHWH2-), even if some of the carbon atoms are in the branch, such as The following is shown in connection with the working examples. For the purposes of the present invention, these are sub-"isomeric"'s. ,

As an example of a particularly preferred compound according to formula I, mention may be made of 1-(triclilorosilyl)-2-(methyldiclilorosilyl)ethane and 1-(Methyldichlorosilyl)-1-(trichlorosilyl)ethane (1-(methyldichlorosilyl)-l-(trichlorosilyl)ethane). Production As mentioned above, a monomer having the formula: is produced in the first step of the process according to the invention:

Wherein & is a hydrolyzable group; 200807705 24699pif R2 is hydrogen; and R3 is a bridged or branched divalent nicotine. This monomer and a similar decane-based material can be produced, and the rhodium hydrogenation reaction is promoted in octacarbonyl cobalt. The fly reaction is carried out in the case of ^ ^ 勹 隹 隹 隹. _ t or any _ transition metal xin

ΓΓΓΓΓ ) The new S f - catalyzed by the catalyst is used as a reactant. Therefore, in order to produce i, w Ding Chu _ in high yield, in the presence of eight techniques, the compound can be reversed with the second two domain Wei compound.

The sect of the company has a group containing a singular and sulphur reactor to aid in the hydrogenation reaction. W is prepared in the example 1, wherein the vinyl trigas and the ground are obtained by the disclosed method to obtain the desired β substance with high purity, and the riding is allowed to be prepared by the & The subsequent step of the oxoxane material uses the monomer as a precursor. The present invention provides an optical dielectric siloxane polymer suitable for use in the form of heat and mechanical stability, high refractive index, optical transparency, high fracture centering, initial, collection and low pore volume and pore size dielectric film . The polymer, after treatment, is processed to produce a film of water-free and stanol with excellent local and global flatness and gap filling, which has excellent electrical properties. It has been found that the film made of polymer f remains structurally, mechanically and electrically unchanged after final curing even at temperatures higher than the final curing temperature. Since all of these characteristics are superior to conventional low dielectric constant polymers, they are critical to the existing problems of the integration of low dielectric constant films into semiconductor devices for the PCT 200807705 24699pif. + 1 ° synthesis is based on hydrolysis and condensation chemical synthesis techniques. The polymerization can be carried out in a molten phase or in a liquid medium. The temperature at which the reaction is carried out is in the range of from about 20 & C to about 2 Torr (TC, usually about 25. 〇 to about 16 〇. 〇, in particular, j 80C to about 15 〇. 〇. Usually, polymerization is at ambient pressure The process is carried out and the maximum degree is set by the boiling point of any solvent used. The polymerization can be carried out in the reflux zone I. In the absence of a catalyst or by the use of basic (or in detail -) catalysis & The instant monomer is a possible c quinone organic siloxane material having a molecular weight of from 500 to 1 Å, 〇〇〇 white = average. The molecular weight may be at the lower end of the range (for example, Sedigree oxygen = 1 ^ or better from 5GG to 8, _g / mc > 1) or have 〇 nr ^ above the range (such as from 10, _ to mixed More from 15, w to 5 °, coffee. 1) molecular weight. It is desirable to have a polymer organic siloxane material in the lower knives and an organic decane material having a higher knives. ϋ It has been found that a suitable polymer composition can be obtained by homopolymerizing a monomer of formula I of the grouping agent group, a spring, or a knife having a formula u with a formula! (The composition obtained by the & represents the first monomer of the branch two is also possible, and the second single ear ratio of the second magic is 95:5 to 5:95, in detail, the body and the second brother In addition, the formula j to 10:90, preferably 80:20 type of early body can also be any ratio with any known can be 200807705 24699pif ^ Oxygen or organic metal ( For example, titanium alkoxide (aik〇xide), titanium telluride, zirconium alkoxide, barium chloride, butyl alkoxide (, " painting (four) heart), chloride, melamine Aluminium alkoxide or chlorinated (but not limited to) monomer copolymerization. According to a preferred embodiment, in order to modify the characteristics, the Wei-burned material deposited on the semiconductor substrate is heated to lead the ship. Cross-linking, whereby a film having a shrinkage of less than 1%, preferably less than 5%, in particular less than 2%, and a thermal stability of more than 425., after heating, is obtained. According to a particular embodiment, The film layer is initially lower than the temperature of about cc. After the spin coating of rrratmg) (4), and the money is exposed to uv spokes at a temperature of less than 4 thieves for S20 minutes. Cured. The curing is carried out for a sufficient period of time to react by the organic substituent having a unit at the position R2. Whether the carcass or the f heat treatment can form a dielectric constant having a size of 4·0 J (3.5 or less of #5), and having a length of I·58 or more in the range of 63 (more specifically, (10) or More rate 'with a Young's modulus of 5.0 Gpa or greater, a low dielectric film with a greater rupture threshold of $, === 4 ^ Using the temperature of the film formed by the polymer, Stable on the semiconductor structure. Woop or more oxy-fired substrate can be doped with nanoparticles to make progress = particles including oxides, semiconductors and metal nano-seconds; compounds such as silk properties, material properties And the machine 200807705 24699pif can modify the nanoparticle by coupling a chemical group on the surface of the nanoparticle. These chemical coupling groups are usually so-called silane-coupling groups, but not limited to The decane coupling element is, for example, amin〇pr〇pyl trimethoxysilane, methacryloxy propyl trimethoxysilane or glycidoxypropyl hydride. Glysidoxy propyl trimetho Xysilane) and other similar groups having a sulphur-burning residue coupled to a functional group. One advantage of using a coupled-treated nanoparticle is that it enhances the solubility of the particle to the oxiranyl group and also enables the particle to be covalently bonded. The number of coupling elements can also be changed at the surface of the nanoparticle. The relative amount of the linking agent can be 1 or higher, and usually has more than one bonding agent molecule on the surface to ensure Sufficient bonding of the polymer matrix is preferred. Typically, the polymer or copolymer is from 1 to 500 parts by weight, preferably from about 5 to about 100 parts by weight, in particular from about 10 to about 50 parts by weight of the nanoparticles. It is combined with 100 parts by weight of the polymer or copolymer to form a composition containing nano particles. The polymer or copolymer can be combined with the nanoparticles by mixing (in other words, mechanical mixing in detail). It is also possible to combine a polymer or a copolymer with a nanoparticle in such a manner that a polymer bond or a copolymer is formed between the polymer or the copolymer. Therefore, the use has the ability to react with the nanoparticle and to form a poly Object It is possible to form a bonded polyisomer or copolymer between the copolymer and the nanoparticle. The use of a decane coupling element of 200807705 24699pif or a group U particle as discussed above is also achievable. It will also enhance the physical properties of the composition, the physical properties of the moths, the optical properties, and the electrical properties. -= (4) The gamma-containing chemically bonded nephew and the k-complex, among which Mixed polymer _ed C_ymer). The natrix is bonded to the mixture 3^;:= component. / ΧΚ σ can be made, for example, by a method selected from the group consisting of an alkaline solution or an acid fire = dissolving hyd kiss sis), a laser siardens, and a combination of two or more of these methods. Nano particles. Honestly, this list does not limit (4) this month, and it will give you any way to get particles of the desired particle size. The particle size (average particle size) may range from 丨nm to several microns, and it is generally preferred to have a particle size of 20 or less (more specifically about 0.5 mn lang 18 Å) in optical and 1C applications. Further, it is preferable that the particle size distribution range is narrow, but it is not essential. Typical materials to be doped to organic siloxane alkyl nanoparticles include, but are not limited to, the following groups: Metals: Fe, Ag, Ni, Co, Cu, Ft, Bi, Si, and metal alloys 0 Metal oxides · Ti02, ZnO, Ta205, Nb205, Sn02, Zr02,

Mg02, Er2〇3 and Si〇2. Carbide: SiC. Nitride · Si3N4, AIN and TiN. In the U.S. Patent Application Publication No. 2005/0170192, the disclosure of the entire disclosure of the disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of Nanoparticles are typically used in the form of dispersions ("dispersions". Suitable sub-agents include water, organic solvents such as alcohols and hydrocarbons, and combinations and mixtures thereof. Preferred solvents are generally selected as nanoparticles. Depending on the characteristics. @本, Dispersants and nanoparticles should be selected to make a good balance with the formation of a good fraction. For example, the fresh pH depends on the crystal structure and surface structure, but gamma The oxidized particles are usually well dispersed at an acidic pH of about 3 to 4, and the cerium dioxide particles are usually easily dispersed at an initial pH of 9 _ n. The titanium oxide particles are usually at a pH close to 7. It is well dispersed. The system has a small surface charge, and the green particles can be dispersed in a small solvent. Therefore, the hydrophobic particles can be dispersed in a non-aqueous (anhydrous) solvent or a scented water towel. The heterolium can be dissolved in the nanoparticle solvent dispersion in water, and the surface of the particle is also reacted with a catalyst. The hydrolyzable portion of the coupling group is especially in the presence of water as water: The invention occurs spontaneously, as mentioned above, and the invention also provides a method of fabricating an integrated circuit. These methods generally comprise the steps of: forming a plurality of transistors on a semiconductor substrate; forming a multilayer interconnect by the following steps: deposition a metal layer; a patterned metal layer; 200807705 24699pif depositing a first dielectric material having a first modulus and a kth value; depositing a second modulus having a first modulus higher than the first material and having a lower a second dielectric material having a k-value of a first-k value of the first material; and patterning the first dielectric material and the second dielectric material, and depositing a via-filled metal material in the patterned region According to the present invention, in the first-dielectric material, there is a material of the company, which has a repeating Μ-0-Μ-0 rhyme with a first organic substituent bonded to the main chain. Having a self-face to (10), a simple 4'0 exhibits one or several of the following characteristics: a k value of 4.0 or less or better than 3 5 or less; : or more = refractive index, or better 16 or greater; 〇ppm or less thermal expansion expansion, CTE); and merma l 4 GPa or greater Young's modulus. Due to the excellent steps of the flattening, the picture is carried out in the case of a peach or a chemical-free flattening. In addition to the total thickness of the second dielectric material, the organic siloxane material can be hydrolyzed by the liquid formed by polymerizing the monomer of the formula I in the form of a bismuth; The hydrolyzate, -:,,, thin layer and solidified thin layer to form a film having a thickness of 200,807,705, 24,699 pif 〇. 〇 to 1 〇 _. or 'organic oxalate material can be - liquid medium towel polymerization〗 $ _ formed by c, a 〇 ^ salt, gasification button, aluminum alkoxide bite gasification ... 1 emulsified 鍅, button alcohol; a ^ ^ current aluminum sulphide (but not limited to this)) The formation of a decane gas material or a mixture of oxalic acid is carried out, and the hydrolysis of the hydrolyzed silk-age genus (4) is known as a thin layer on the substrate and the thin film having a thickness of from 0.1 μm to 10 μm is cured. Ear (three) field

In view of the fact that one of the dielectric materials comprises a material according to the invention, the further material may be a known organic, money or organic/inorganic material, such as the ones discussed in the introductory section. Typically, the organic siloxane material is a spin-on material. The organooxane material is organic-inorganic and has a coefficient of thermal expansion of from 12 Ppm to 3 〇 PPm. It may have a refractive index of 16 or less. Additional details of the invention can be discussed in conjunction with the following working examples: Example Example 1 1,1,1,4,4-pentachlorodioxane (intermediate) Wide SiCI3 + H2SiCI2

Co2(CO)e^ 〇°C...rVl5h CI3Su , SiHCl2 Ethylene trichloropyrene (68·8 g, 426 mmol) and octacarbonyl (700 mg) were placed in a 100 mL rb flask, and Cool to 200807705 24699pif 〇 °C in an ice bath. Diclosure (bp·8°C, 44·3 g, 439 mmol) was then condensed into the flask. The system is allowed to heat to room temperature during the night. At 60. Distillation was carried out at 〇/8 mbar to 62 °C/8 mbar, while 1,1,1,454-pentachloro-1,4_2 石 丁 烧 (120.8 g, 460 mmol) was given at 93% yield. Example 2 Tris(3,3,6,6,6-pentachloro-3,6-dihexyl)chlorosilane (tris(3,3,6,6,6-pentachloro-3,6_disilahexy)chlorosilane) 3 CI3S, \^S(HC(2 + ClSif^)3

HgPtCle/[PA 110°C / 60min 〇I3Si

11.00 g (0.076 mol) of trivinyl chlorodecane followed by 2 ml of 1,1,1,4,4-pentachloro-1,4-diazepine was added to the container of i〇〇 ml. The solution was heated to 80 ° C, and 10% of H 2 ptCl 6 /Ip of I5 μί was added: a strong exothermic reaction was observed, and the heat source was cut off. Keep the solution temperature below 130. . In the state, the total amount of 1,1,1,4,4-^ ^ Ua,4,4-ia.l54.^^T^ is slowly added during the period of 30 minutes to be 61.50 g (0.234 mob 2.6%) excess). After the addition of the heating source is turned on again, and the solution is mixed under 1HTC-hour distillation solution to obtain the pendulum g (66%) of the three (3,3,m,6_pentachloro-200807705 24699pif-stone-hexyl) chlorite burn. Β·ρ· 264°C/<0.5 mbar. Example 3 U,l,4,4,7,7,7-octachloro-1,4,7-trioxane (1,1,1,4,4,7,7,7-octachloro_ 1,4 , 7_trisilaheptane).瞵_.SiCI3 1_6 is called CI3Siv^v^/N^SiCI3 2 90°c/12h ^ Ethylene trichlorodecane (16.8 g, 104 mmol) is heated to 60 ° C and 100 gL of 1% H2PtCl6/IPA is added Solution. 1,1,1,4,4-pentachloro-1,4-dioxane (20.4 g, 77.7 mmol) was slowly added over a period of 20 minutes so that the temperature did not exceed 10 CTC. The reaction was allowed to proceed for 12 hours at 10 °C, after which it was distilled under vacuum at 115-130 ° C / < 1 mbar. The yield was 31.5 g (74.3 mmol > 96%) ° Example 4 1,1,1,4,4,7,7,7-octane-1,4,7-trioxane (1,1,1 ,4,4,7,7,7_octachloro_ 1,4,7-trisilaoctane) cfeSisSfc/^s(Hcl ψ c^J^SiCI2 JjpptCl5/lPA Cl3Si 2 90°C; 1.5h ^ 1,1,1,4, 4_Pentachloro-1,4-dioxane (51.6g, 196mmol) was added to 200807705 24699pif to 80 ° C and 20 g of 10% H2PtCl6/IPA solution was added. Vinylmethyl group was slowly added during 20 minutes. Dichlorodecane (29.7 g, 210 mmol) such that the temperature does not exceed 130 ° C. The reaction is allowed to proceed for L5 hours, after which it is distilled under vacuum at 90-102 ° C / < 1 mbar. Yield 70.2 g ( 174 Ment, 89%) 〇Example 5 to 7 1,1,1,4,4-pentachloro_1,4_ dioxin (1,1,1,454_pentachloro-1,4_disiladecane) 1,1,1,4 , 4-penta-1,4-dipod 12 (1,1,1,4,4-pentachloro 1,4-disiladodecane) 1,1,1,4,4-pentachloro-i,4- Ershi Xi-14 (1,1,1,4,4-pentachloro 1,4_disilatetrakaidecane)

SiHCI2 H2PtCl6 / IPA 0j3sjs 11〇°C/1h

Cl, 扣 32 ml (21.53 g, 0.256 mol) 1-hexene and 2 〇 吣 IPta^iPA Lin was added to a 100 ml container. The solution was heated to 8 ° C ' and slowly added 46.90 g (〇.l79m〇l) of 1,1^1,4,4-penta-l,4-dioxane during f minutes. When an exothermic reaction is observed, the two = force is cut off; the temperature during the period remains below the assignment. After the addition, the solution was stirred for one hour at -10 °C. Thereafter, the product was purified by distillation. B 1〇〇. (8) Adjustable by ^^/〇.8 and. The yield was 5 〇, j octene or I decene was replaced to produce 1,1 s, 4, 4-, 5, 4, 4, and 2, rk 7 undecane (bP131 ° C/0.7, respectively) The yield of mbar, 88% 200807705 24699pif) and 1,1,1,4,4-pentachloro-1,4-dihydrotetradecene (bpl 38 ° C / 0e8 mbar, 82% yield). Example 8 1,1,1,4,4-Pentachloro-7-phenyldiazepine (1,1,1,4,4,pentachloro,7_phenyl-1,4-disilaheptane)

cl3Si~f^O

18.77 g (0.159 mol) of aiiyibenzene and 50 pL of HsPtCVIPA solution were added to a 100 ml container. The solution was heated to 80 C and 41.85 g (0.159 mol) of U,l,4,4-pentachloro-1,4-dioxane was slowly added over 30 minutes. When the exothermic reaction is observed, the heat source is turned off. The temperature during the addition was kept below l30〇c. After the addition, the heating source was turned on again, and the solution was stirred at 110 ° C for one hour. Thereafter, the product is purified by distillation. Β·ρ· 137. <3/0.8 mbar. Yield 35.10 g (58%) 实例 Example 9 1'1,1,4,4-pentachloro-6 pentafluorophenyl_ι,4_二石夕己烧

(1,1,l,4,4-pentachloro-6-pentafluorophenyl-1,4-disilahexane) 200807705 24699pif 116.15 g (0.442 mol) 1,1,1,4,4-pentachloro-1,4-dioxene Butane was added to a 250 ml vessel followed by loo pL in H2PtCl6/IPA solution. The solution was heated to 85 ° C and 85.80 g (0.442 mol) of pentafluorostyrene was slowly added over 30 minutes. After the addition, the solution was stirred at 100 ° C for one hour and then distilled. BP. 122 ° C / < 1 mbar, yield 158.50 g (78%). Example 10 1,1,1,4,4-pentachloro_ι,4-二石石-5-hexene (1,1,1,4,4_pentachloro 1,4_disila_5_hexene) C[3Si 〇〇2(C〇 )g 0pC/15h

Cl Cl 40.00 g (0.152 mol) 1,1,1,4,4-pentachloro-1,4-diazepine was dissolved in 1000 ml of 1,4·dioxane in a 2000 ml container (i , 4-dioxane). The solution was cooled to 〇 ° C and acetylene was poured into the solution to cause foaming until it was saturated. The solution thus obtained is slowly heated to room temperature. The cauterization was evaporated and the obtained crude U,M,4_pentachloro-indole, 4_diindole-5-hexene was purified by evaporation. Example 11 1,1,1,4,4-Five Rat-7-(3,5-Dimethyl Foundation! 1 alkyl)-1,4_二石夕::: End (1,1,M ,4-pentachloro-7-(3,5-dimethyladamantyl)-1,4-disilah 31 200807705 24699pif eptane)

81.71 g (0.336 mol) 3,5-dimethyladamantyl bromide (3,5-dimethyladamantlybromide) was dissolved in 5 〇q mi. The solution was cooled from an ice/acetone bath to below -lot. 51e4〇 g (0.425 mol) of alliyibromide was added, followed by the addition of 410 mg of FeBr3. The solution was then stirred at -20 ° C to 10 ° C for three hours, after which it was analyzed by gas chromatograph-mass spectrometry (GC-MS). The results showed some unreacted raw materials remaining. . 420 mg of FeBr was added; 3 and the solution was stirred for an additional two hours, after which the results of GC-MS showed that all of the dimethyldetane bromide had reacted. The solution was warmed to room temperature and rinsed twice with 500 ml of water. The organic layer was collected and evaporated to dryness. The remaining material was dissolved in 7 〇〇 mi of ethanol, and a small amount of water was added, followed by the addition of 25 g (〇·382 mol) of metallic zinc. The solution was then heated to reflux and stirred for 15 hours. After cooling to room temperature, the solution was filtered. 3 〇〇 ml of water was added and the product was extracted by rinsing twice with 500 ml of pentane. The pentane layer was collected and rinsed once with water. The organic layer was collected, dried over anhydrous magnesium sulfate, and then filtered. The pentane was evaporated and the remaining crude 丨-allyl_3,5-dimethyl fund was purified by distillation to yield 45.90 g (67%). 1-Allyl-3,5-dioxanecone was transferred to a 100 ml vessel followed by 50 juL of HJtCVIPA solution. The solution was heated to 85 ° C and 59.50 g (0.227 mol) of ι, ι, ι, 4,4-pentachloro-1,4-dibutane was slowly added over a period of 3 Torr. After the addition, the solution was heated to 10 ° C and stirred for one hour. The product thus obtained was then purified by distillation to give 53.54 g (51%) yield, bp. 157-158 ° C / < 0.5 mbar. Example 12 1,1,1,4,4-penta-5,6-dimercapto-1,4-diazepine-6-glycol (1,1,1,4,4-pentachloro_5,6_dimethyl- 1,4_disila-6_heptene)

(Ph9P) aPd(0) 80 ports C/1h

49.85 g (0.190 mol) 1,1,1,4,4_pentachloro-1,4-dioxane was added to a 100 ml vessel followed by about 20 mg to 30 mg of tetrakis (triphenylphosphine) )! (O) (tetrakis (triphenylphosphine) palladium (0)). The solution was heated to 80 ° C and 13.10 g (0.192 mol) of isoprene (iso-prene) was slowly added over 30 minutes. After the addition, the solution was at 1 Torr. The crucible was stirred for one hour and then distilled. Bp 96 ° C / < 1 mbar, yield 58.50 g (93%). If the same reaction is carried out with a H2PtCl6/IPA catalyst at 80 °C or with a Co2(CO)8 200807705 24699 pif catalyst at room temperature, a 1:1 hazardous compound of the alpha and beta substituted isomers is obtained. Example 13 U,l,4,4-Pentachloro-6-(5-norborn-2-ene)-1,4-dioxane (1,1,1,4,4_pentachloro_6-(5-norborn- 2_ene)_ 1,4-disilahexane) CI3Si>, SiHC [2

H^tCb/lPA 10CTC/1h ^ 22.63 g (0.086 mol) 1,1,1,4,4_pentachloro_1,4_二石丁丁烧 was added to a 100 ml container, followed by 70 pL H2PtCl6/IPA solution. The obtained solution was heated to 85 t, and then 10.81 g (0.090 m〇l) of 5-vinyl-2-norbornene was slowly added over 30 minutes. After the addition, the solution was at 1 Torr. (: The mixture was stirred for one hour, and then distilled. Βρ·140. (:/<1 mbar, yield: 20.05 g (61%). Example 14 9. Non-based ethoxylated triethoxysilane

Mg TEOS

THF

Si(OEt)a

200807705 24699pif 5.33 g (0.219 mol) of magnesium and a small amount of iodine were added to 1 such as glutinous rape, followed by 56.38 g (〇·2ΐ9 丨) 9-bromophenanthrene. 196 ml ( 182.74 g, 877 877 m〇1),

Si(OEt)4 was added to the valley state. Adding 200 mi of thj?, an exothermic reaction occurs after that. After the solution had cooled, it was heated to reflux and stirred overnight. The reflux was stopped and 300 ml of η-heptane was added. The solution was poured into a separate container and the remaining solid was rinsed twice with 200 ml of η-heptane. The rinse solution is added to the reaction solution. THF and η-heptane were evaporated, and the remaining material was subjected to distillation. Β·ρ· 175 C/ 0.7 mbar. The yield was 52.63 g = 70%. Example 15 1_(9-phenanthryl)-1,1,4,4,4-pentamethoxy-oxime, 'di-butane (1-(9-phenanthrenyl)-15194?454.pentamethoxy-154-disilabutan e)

^Si(0Me)3 ^Si(0Me)3 OMe

Mg THF

MeOs

kS!^-SH〇Me N〇Me OMe 7·23 g (0.297 mol) of magnesium and a small amount of iodine were added to a 1000 ml vessel, followed by 56.38 g (0.219 mol) of 9-bromophenanthrene. Bis (trimethoxysilyl) ethane (237 g, 0.876 35 200807705 24699 pif of THF. In a few minutes ' it was heated to reflux 1) was added to the vessel, followed by An exothermic reaction occurred within 200 mj. After the solution has cooled and is disturbed overnight. The reflux was stopped and 300 ml of η-heptane was added. The solution was poured into a separate container and the remaining solid was rinsed twice with 200 ml of η-heptane. The rinse solution is added to the reaction solution. THF and η-heptane were evaporated, and the remaining material was distilled. Β·ρ· 190-205°C/<0.1 mbar. The yield was 59·23 g = 65% 实例 Example 16 3-(9-phenanthrenyl)propyl trimethoxysilane

36 200807705 24699pif

6·9〇 g (0.284 mol) of municipal powder and a few moth crystals were added to a 1000 ml vessel, followed by 73.07 g (0.284 mol) of 9-bromophenanthrene. 90 ml of THF was added, and an exothermic reaction occurred after that. When the solution had returned to room temperature, 30 ml of THF was added and the solution was heated to 65. (: and was stirred all night., Allow the solution to cool to 5 〇 it, and 34.42 g (〇·285 m〇1) of allyl in the minute, turn the silk liquid gradually back to the red material is dripped in ~ After the addition, the solution was stirred for 2 hours at 65 c. The solution was cooled to room temperature and most of the THF was removed by direct mediation. 700 ml of DCM was added and the solution was moved to the separation funnel. The solution was rinsed twice with water of ML. 200807705 24699 pif The organic layer was collected and dried over anhydrous magnesium sulfate. The solution was filtered, and then solvent evaporated. The remaining material was purified by distillation. B p. lmi5t: / < 5 mbar. The yield was 54.5 g (88%). Allylphenanthrene (41.59 g, 〇·ΐ91 mol) was added to a 250 ml round bottom flask and heated to 9 〇t: Add %卟之10% H2PtCl6/IPA. The addition of HSiCl3 was started and the exothermic reaction was observed. The addition of hydrazine was slowly added during 40 minutes. After the addition, the amount of HSlCl3 was removed by vacuum when the stirring m was applied, and 1 〇〇 Methyl (97 g, 〇 914 m〇i) trimethyl ortho-acid I (tnmethyi orth () f () rmate) was added, followed by 5 mM of BmPCl was added as a catalyst. The solution was stirred at 7 Torr: 9 hr, and the product was purified by evaporation. Β·ρ. 172t: /<Q.5 mbar. Yield 5 〇g (based on 74% of the amount of allyl phenanthrene. Example 17 South refractive index polymer 1, phenanthrene-ethoxy ethoxylate (15 g, 44 mmol), acetone (22.5 g) = =·01Μ Η=1 (7 · 2 g ' _ mmd ) placed in _ mL of rb W ' and refluxed for 23 hours. Volatile under reduced pressure = compound (n.84g). Polymer in service A (, ^ ^ 》 privately. _ lower soft for training _ baice) 5 knives 4 miles 'then in the feeding range is 1 6680c:=, the refractive index is 632.8 鈇, and take 仏,, · The dielectric constant is 3.5 at 1 MHz. ♦ σ目For the 彳 有机 有机 有机 200 200 200 200 200 200 200 200 200 200 200 200 200 807 200 200 200 807 807 807 807 807 200 200 200 200 807 807 807 807 200 807 807 807 807 200 807 807 807 200 200 200 200 200 200 200 200 200 200 200 200 200 Prepared by the Grenner reaction between 9-bromophenanthrene, magnesium and tetraethoxydecane in the booklet, and acetone (i5〇〇g) by stirring until the solid limb dissolves. Subsequently, dilute nitric acid (0·01ΜHN〇3, 6.77 g, 0.38 mol) was added. The two phases (aqueous phase and organic phase) are separated. The system was refluxed until the solution became clear (about 15 minutes). Glycidyl xypropyltrimethoxysilane (3 〇〇g, 〇 〇 1 m〇i) was added and chilled for six hours. The volatiles were evaporated in a rotary evaporator until 25.00 g of polymer solution remained. N-propyl acetate vinegar (4) sinking) (32.50 g)" was added, and evaporation continued again until 27 g remained. Next, propanol-monomethylhydrazine-acetic acid vinegar (pr〇pylene galaxies 1 galvanic: ac_e, PGMEA) (3〇g) was added and evaporated again until 24.84 g as a viscous polymer . The amount of non-volatiles was measured to be 69.24 / 〇. Etoposide PGMEA (8.89 g) was added to give a solids content of about . The solution was heated in an oil bath (165 ° 〇 and refluxed for 4 hours ^ 2 = clock. The water formed during the reaction was removed from the PGMEA in the rotary evaporator until 18 g remained. More PGMEA (42 g) It is added so that the solution has a solid content of 22.16%. The polymer has Mn/Mw = 1,953/2,080 g/m〇I. The above results are infiltrated by the gel relative to the monodisperse polystyrene standard. The chromatograph was measured by 3〇200807705 24699pif (glycidyloxypropyitrimethoxysilane, GPC). Sample preparation: The above solution (9.67g) was PGMEA (5·33 g), surfactant (BYK-307 from BYK_Chemie, 4 mg) and Formulated with a cationic initiator (Rhodorsil 2074, 10 mg). It was spin-coated at 4 rpm on a wafer at 2,000 rpm. The film was soft baked at 130 ° C for 5 minutes at 200 ° C. The film was cured for 5 minutes. The film thickness after curing was 310 nm, and the refractive index was 1.66 at 632.8 nm, and the dielectric constant was 3.4 at 1 MHz. The film layer did not dissolve in acetone, which showed cross-linking ( Cross-linking) has been successful. Similarly, a more concentrated PGMEA solution (solids 25%) Prepared, spin coated and cured. The film layer was 830 nm thick and measured by nanoindentation (nan〇incientati〇n) with a modulus of 7.01 Gpa and a hardness of 0.41 GPa. Example 19 High refractive index polymer 3 Base)-1,1,4,4,4-pentamethoxy-, 4-dioxane (9.55§, 22.9 mmol), 9-# bis-ethoxylated (9.02 g, 26.5) Methyl) and SLSI grade acetone (14.0 g) were placed in a 250 ml rb flask with a Teflon coated magnetic stir bar. Distilled water (6.0 g, 333 mmol) was added and the system was refluxed for 15 min. Subsequently, 2 drops of diluted HC1 (3.7 w-%) were added dropwise. The solution became homogeneous within two minutes, which showed the progress of hydrolysis. A solution of 1_(9-phenanthryl)-1,1,4,4,4-pentamethoxy-1,4_bis-xanthene (11.45 g, 27.5 mmol) dissolved in acetone (16.0 g) was injected. This was followed by the addition of 0.01 M HCl solution (8.4 g, 466 mmol). Allow the reaction to reflux 14 200807705 24699 pif hours. After refluxing, all volatiles were removed in vacuo to yield 28.1 g of dry polymer as a colourless solid. It was thermally stabilized in argon up to 500 ° C by thermogravimetric analysis (TGA) (Fig. 2). The solid was diluted in n-butyl acetate (NBA) (73.06 g, 260%) and a surfactant (56 mg 'Byk-Chemle's BYK®-307). Alternatively, a solution of pr〇Pylene glycol monomethyl ether acetate (PGMEA, 240%) and methyl ethyl ketone (MEK, 400%) was also prepared. The NBA solution was filtered through a 〇·2 μ Teflon filter and spin-cast on a 4” Shi Xi wafer at 3000 rpm. Soft bake at 150 ° C for 5 minutes and soft bake at 200 t: 5 minutes, followed by curing in an n2 environment at 400. Under the crucible for 15 minutes to obtain a film having a refractive index of 1.6511 at 632·8 nm and a thickness of 683 nm. The dielectric constant of the film is at 1 MHz. 3.4. A film having a final thickness of up to 1850 nm is prepared and does not exhibit cracking characteristics. The film layer can be rubbed against organic solvents such as acetone without damage. Example 20 South Refractive Index Polymer 4 _ 3 (9-phenanthryl) propyl tridecyl oxide (g, 32.4 mmol), propionate (16. 5 g), and q qimHC1 were placed in a 100 ml rb flask, and: Ϊ, 16 hours. Initially, the solution was milky white, but β was broken shortly after the start of hydrolysis. When the polymerization proceeded further, the solution again became slightly mixed with 200,807,705, 24,699 pif turbid. The volatiles were removed by evaporation under reduced pressure to give a white colorless powder. · 6 〇g. The polymer is stable under argon up to 45 经由 by TGA 1. 3). The casting solution dissolves 2 〇 6g of polymer ' and (4) G. 2 μ of iron by 8.24 g of methyl ethyl hydrazine (4 %) and a surfactant (5 mg, byk, 3 〇 7 of Byk_Chemie) The fluorocarbon filter was filtered to prepare. The polymer was spin-washed on a 4" Shi Xi wafer at 3000 rpm. Soft bake for 5 minutes under i赃, then in the n2 environment. The curing was carried out for 5 minutes under c to obtain a film having a refractive index of l671ijfMi R 0 / ί Λ Π 1·671 at 632.8 nm and a thickness of 840 nm. The dielectric constant of the film layer is at! At 4 MHz, it is 3 4 . The film layer does not show rags. The film layer can be used without any exaggeration. Example 21 High refractive index polymer 5 9-phenanthryl triethoxylate (17 〇〇g, 〇〇5 _, dissolved in the lion until solids. Then add rare stone Xiao ^^ brain 3, 6.77^ .38111. 1). Two phases (aqueous phase and i 1 money reflux until the solution becomes clear (about 15 minutes)., water glycerol minus propyl trimethoxy number (3. (8) g, said coffee and the flask is refluxed for six hours. Volatile in Rotate § +. Cold liquid. N-propyl acetate (32.50 g) 娀 口 ' and continue evaporation again until 27 g remaining. Next, propylene glycol monomethyl 42 200807705 24699 pif ether acetate (30g) was added, and again Evaporation until 24 84 g remained as a viscous polymer. The amount of non-volatiles was measured to be 69.24%. More PGMEA (8.89 g) was added to give a solids content of about 5%. The solution was heated in an oil bath ( 165. and reflux for 4 hours and 2 minutes. The water formed during the reaction was removed from the PGMEA in the rotary evaporator until Μg remained. More PGMEA (42 g) was added to give the solution 22 • 16% solids content. The polymer has Mn/Mw = 1,953/2,080 g/md, and the above results are measured by GPC relative to the monodisperse polystyrene standard in THF. 14% of PGMEA solution Preparation and curing of the catalyst (〇·3%, Rhodorsil 2074 from Rhodia) and surfactant • 2%, from BYK_Chemie ΒΥΚ 307) was added. The material was spin-coated on a ruthenium wafer and cured at 200 C for 5 minutes. The film layer could be cleaned with acetone without damage and showed successful cure. Fourier transform infrared spectroscopy (FTIR) shows that the amount of stanol is very low (a wide peak at 3200 cnT1 to 3800 cnf1). If a curing catalyst is not used, the film will not cure and will be C. In addition, the peak value of stanol in FTIR is high. Example 22 Mixture of polymer 5 and rutile Ti〇2 nanoparticle Preparation of concentrate of polymer 5 and rutile Ti〇2 Nanoparticles (from the trade name 'ns〇l] 〇i-5K from NanoGmm, dissolved in 5% in Mek 43 200807705 24699pif) were formulated such that the polymer/particle mass ratio was changed from 3/1 to 1/3. A surfactant (from 307 of BYK_Chemie _307, 0.2%) and a cationic initiator (Rhodorsil 2074, 0.3%) were added to each sample. It was spin-coated on a 4 Å wafer at 2000 rpm. The film is at 130. Soft baking under the armpit The film thickness (Tx) and refractive index (RI) were summarized in Table 丨 for 5 minutes and at 2 。. The reference sample diluted with PGMEA was used to form a film layer having a thickness of about 400 nm. Table 1: Material mixing ratio 130〇C/5 130〇C/5 200〇C/5 200〇C/5 S% w/w min after min after min min after min Tx RI Tx RI polymer 5 (ref·) - 424 1.67 409 1.66 3.5 Polymer 5-Ή02 3-1 744 1.71 732 1.71 1.6 Polymer 5 - Ti〇2 1-1 322 1·76 313 1.77 2.8 Polymer 5-Ti〇2 1-3 177 1.85 170 1.86 4.0 As can be seen from Table 1, the RI of the material increases as the Ti02 load increases. It can also be seen that the shrinkage rate does not change significantly. Example 23 = Preparation of a mixture of Compound 3 and rutile Ti 2 Nanoparticles ♦ 5 Solution 3 (in 17% dissolved in MEK) in the same ratio as in Example 22 in a weight ratio of 1-2 Mix 5% Ti〇2 solution. The solution was evaporated back to a solids content of about 17%. The solution was spin-coated at 2 rpm, and 200807705 24699pif was then soft baked at 150+200 °C for 5+5 minutes and cured at 300 °C for 15 minutes. The results are shown in Table 2. Table 2: Material Mix Ratio 150+200°C 150+200°C 300°C/15 300°C/15 S% w/w / 5+5 min / 5+5 min min After min After Tx RI Tx RI Polymer 3 (ref·) · 846 1.66 822 1.65 2.8 Polymer 3 -Ti02 1-2 549 _ 511 1.85 7.0 As can be seen, the polymer-rutile Ti〇2 nanoparticles are 丨_2 At the ratio, the refractive index of the film layer is increased by 〇·2 units. Example 24 Preparation of a mixture of polymer 5 and anatase Ti 2 nanoparticles Polymer 5 was obtained at a solid ratio of ι_ι and i_3 with anatase Ti 2 nanoparticles (from Sumitomo under the trade name 'ZRM_001, , mixed with 12% in MEK). The film was baked at 2 〇〇 π for 5 minutes. List the results in Table _ 3. 45 200807705 24699pif Table 3: Material mixing ratio 130〇C/5 130〇C/5 200〇C/5 200〇C/5 w/w min after min after min min after polymer 5 (ref.) polymer 5 -Ή〇2 Polymer 5-Ti02 Μ 1-3 Tx 424 ΝΜ ΝΜ RI 1.67 ΝΜ ΝΜ Tx 409 910 591 RI 1.66 1,73 1.80 s% 3.5 As can be seen in Table 3, the refractive index of the film Increase with increasing anatase. ', 乂 All high refractive index polymers have also been tested for trench gap fills with trenches of 丨 (width) χ 4μηι (height). All polymers are in the ring ^ and are in the process. (: Excellent kinetics of gap filling after 5 minutes of squatting. Ears also found all high refractive index = 1-5 compatible with CMP (Chemical Mechanical Grinding). It has been found in conventional oxide CMp paste (4) ^ = Before CMP, the effect of additional higher temperature curing was first applied to the solid layer and then at 丄C to 450 C. When first at a lower temperature, the film was only partially cured ( That is,:)). Due to Lai, the polymer film is still light. "The above conditions are better when performing the oxide CMP process. The use of oxygen plasma is also compatible with the etch back process. When oxygen is applied When plasma: Reason - causes any change in reaction index, surface roughness II = 46 200807705 24699pif. It is worth noting that conventional high refractive index organic polymers cannot be used without damaging the surface quality of the film layer or changing the optical properties of the film layer. In the case of CMP and etch back. The new generation of CMOS image sensing that can be achieved by the chemical treatment mentioned above (Fig. 1) also has three important technical problems: device size, speed, power consumption, and quantum efficiency. Interpretation: 10 semiconductor substrates; 2 Photodiode; 3 f gold f-line, mter-iayer die- ties (ILD) and inter-metai dielectric (IMD) ·, 40 color enamel array re- (four) lens array; Filled with high aspect ratio (4) (10)) Photoelectric = bulk refractive index high refractive index siloxane polymer; 2 高 high refractive index siloxane polymer for color filter planarization and protection; and 3 〇〇 protection micro The lens of the helium oxide polymer. Device size: the smaller the pixel, the greater the number of pixels on the same area (ie, the improved field factor (fleldfact〇r)). This can be achieved by reducing the lens size, the diode Size, thinner metallization and coating of multiple metal layers to achieve. Speed · Shorten the metal wire, improve the conductor, and reduce the k value of the dielectric to improve the speed and reduce the power consumption. Efficiency · This is an opportunity to improve efficiency by using a new material that carries light into the lens and transmits the light to a polar body. The material is deposited before the color filter array and its mechanical properties are set at a relatively high temperature. And other materials used for wafer construction towels The material deposited after the deposition of the phase film must be fully cured at a lower temperature '', c or below). The material of the present invention is very strong. 47 200807705 24699pif Suitable for applications above and below color filter arrays Maximize the quantum effect D on the Wei (4) and the color filter and transmit it to the diode in the skirt layer. The goal is to maximize the amount of light to the body. For example, directly The second of the diodes is transparent and transmits the maximum amount of light. The side of the material 100 in Figure 1 ^

The surface is the source of light loss due to refraction and reduces reflection to the diode G light. A simple solution is to line the sidewall with a reflective coating, but the approach will add cost and will be very difficult. Moreover, the CVD gold II reduces the light transmission and eventually pinches off at the top due to the narrow features; 1 more if the material 100 has a more folded material than the material used to form the wall immediately adjacent thereto; strict: minimizes refraction and More light will be directed to the diode. Therefore: A generaization is formed by the side for the first channel

The oxide has approximately 14 = CVD in the (10) „m wavelength range. It is required to have a refractive index of Μ.46 to reduce interface collapse, which is basically a vertical waveguide that transmits light to the diode. The high refractive index of the polymer from the example Μ is based on the neighboring ==, .2 = .\. Since 4, the film and therefore will be mechanically low temperature, but its: the required process: = more "and the reduction of the genus, the speed of improvement, so the second set is smaller and the gold / care and lens protection: 48 200807705 24699pif material (2GG in Figure 1) on the color filter array for device performance The cost reduction is different. The polymer from Example 18 made visible light permeable and effectively blocked. &曰 Therefore, the photoprotective color filter and the diode are both as well as: The polymer from Example 18 is an excellent planarization material tantalum layer. The polymer also matches the color filter layer at the Caesar rate, thus reducing the reflection from the film interface. Refraction between layers = cured and 'so does not cause organic color: material: [Simple description of the diagram] Figure 1 shows a CMOS image sensor device Figure 2 shows a pyrolysis of a high refractive index polymer 3 . Figure 3 shows the pyrolysis of the high refractive index polymer 4. Figure 4 shows the refractive polymer 5 〇, [Key Field Symbol Description] Cutaway. 20 30 40 50 10: Semiconductor substrate photodiode =, layer germanium: dielectric and metal color filter array layer microlens array 10 () filled with high aspect ratio photodiode between polymer body 1 gap Refractive index 矽 alkane 2 (10) for color filter flattening polymerization and edge-retaining high refractive index helium 300: protection of microlens shixi oxygenated polymer 49

Claims (1)

200807705 24699pif Patent Application Range: 1. A semiconductor device comprising: a semiconductor substrate; a photodiode disposed in the semiconductor substrate, a layer of metal lines and a dielectric (4), the surface of which is red Connecting the interconnecting layer to define an aperture at the photodiode; the first polymer 'fills the gap to cover the photodiode. The slice is opposite to the photodiode Disposed on the gap-filling polymer layer; a second polymer disposed on the interconnect layer to densify and protect the color filter layer; a plurality of microlenses relative to the color a second polymer on which the filter is flattened; and a micro-transparent layer disposed on the microlens to protect at least one of the polymer materials comprising a gas-oxygenated polymer. , _2. For the towel, please use the semiconductor device described in the article, and the two kinds of polymer materials are organic Weiqi compound. - 3. In the case of the semiconductor device described in the first paragraph of the patent application, 1 zhong == compound contains Wei shouting compound, · residual ^ f Sl-〇_Sl_ and · Si-(CH'Si-based a group, wherein X is a number of ! or 2 and y is an integer between 1 and 2 。. 4. The semiconductor device according to claim 3, wherein the three polymers in the basin are Containing Wei green compound, job money green ^ object 50 200807705 24699pif There are -Si-O-Si- and -Si_(CHx)y-Si· groups, where x is an integer of 1 or 2 and y is between 1 and 20 The semiconductor device according to any one of claims 1 to 4, wherein the polymer has a refractive index greater than 1.58 at a wavelength of 632.8 nm or higher. 6. The semiconductor device according to any one of claims 1 to 4 wherein the polymer has a refractive index greater than 1.65 at a wavelength of 632.8 nm or higher. ',; 7. If you apply for a patent scope! To a half-receiving device, wherein the polymer has a refractive index greater than 1.60 at a wavelength of 632.8 nm or higher, and a dielectric constant of 4.0 or lower. 8 as claimed in the patent application. The engraving apparatus of any one of the items, wherein the polymer has a refractive index of a large thick 1.60 at a wavelength of 632.8 nm or higher and a dielectric constant of 3.5 or less (1; 9; The semi-conductive device according to any one of claims 1 to 4, wherein the polymer has a refractive index greater than 1.60 at a wavelength of 632.8 nm or higher, and a Youngs with a height higher than 4.0 Gpa Modulus '. 10. The semiconductor device described in claim 1, the potted polymer is thermally cured at a temperature between 180 ° C and 450 ° C / 11 · as claimed in the patent scope The semiconductor device of claim 10, wherein the polymer is cured by a combination of heat and ultraviolet rays. The semiconductor device of claim 10, wherein the polymer is thermally cured first It is then treated by chemical mechanical polishing. 51 200807705 24699pi The semiconductor device according to claim 10, wherein the polymer is first thermally cured, and then subjected to a dry etching plasma process. The semiconductor device according to any one of the preceding claims, wherein the polymer is processed by the ultraviolet ray process. The semiconductor device according to any one of claims 10 to 13, wherein the polymer is first Thermally cured, and then further processed by chemical mechanical polishing, and then subjected to final heat or ultraviolet curing. 16. The semiconductor device according to claim 1, wherein at least one of the polymer and color filter The light sheet layer or the microlens layer has a refractive index difference of less than 0.1 in the visible light wavelength range. 17. The semiconductor device according to claim 16, wherein at least one of the polymer and the color filter layer or And a microlens layer having a refractive index difference of less than 0.05 in the visible light wavelength range. 18. The semiconductor device according to claim 1, wherein the first polymer has a boundary The semiconductor device of claim 18, wherein the first polymer has at least 5 higher than the material defining the aperture. The semiconductor device according to claim 1, wherein at least one of the polymers comprises a chemical structural formula: 52 200807705 24699pif si -Si, Ri^Si anti 1 : tl is hydrolyzable a group; an organic group or a group, a reactive cleavage group, a polarizing group, an aryl group, a combination of multiples, a group of a W-based group, a block group, and an organic group. And 3;,,, t telecommunication or branched or polycyclic groups. The scutellaria-mercapto group, polyaromatic Μ 如 如 如 如 如 如 如 如 如 如 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物The device, wherein the semiconductor according to the polymerization item is placed, wherein the human, the β 1 injured nanoparticle and the 10 Å by weight of the mouthpiece, and the sputum form a composition containing the nanoparticle. In the semiconductor device according to Item 22 of the patent application, the small-sized substance in the pot is combined with about 5 to 10 (10) and the polymer is combined to form "'...4/100 parts by weight. Such as the patented composition. The polymer is a simple semi-conducting material, in which the material is incorporated into the IV nanoparticle and 100 parts by weight of the composition of the nano-teacher. The invention is as described in claim 2 The rice particles are semiconductor devices selected from the group consisting of metals, &<RTIgt;