TWI473255B - Semiconductor optoelectronics devices - Google Patents

Description

Semiconductor optoelectronic device

The present invention relates to a process for fabricating a semiconductor device by utilizing a novel polymer. In particular, the present invention provides novel semiconductors in which at least one optical layer or electricity of a complementary metal oxide semiconductor (CMOS) image sensor is fabricated using a polymer or polymer composition of a functionalized decane monomer. Floor. Furthermore, the present invention is directed to integrated circuits and optoelectronic devices and methods for processing novel polymeric materials when fabricated therefrom.

The commercial use of electronic image sensors in electronic technology has increased dramatically in recent years. Electronic image sensors can be found in cameras, cell phones, and new security devices for automobiles (eg, for estimating distance between vehicles, detecting blind spots that are not exposed by mirrors, etc.). Many semiconductor manufacturers convert production lines to CMOS sensor production to meet this demand. CMOS sensor fabrication uses many of the processes currently used in the manufacture of standard integrated circuits (ICs) and does not require large capital investments to produce devices of the current state of the art.

In the bottom-up process, the photodiode is placed in the germanium layer. Standard dielectric and metal circuits are placed on the diode to transfer current. The optically transparent material disposed directly on the diode is an optically transparent material that transfers light from the surface of the device and through a color filter to the active photodiode. Transparent protection and planarization materials are typically placed on color filters and devices. The microlens is placed on a flattened film layer on a 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 left between the lens and the cover. Most CMOS sensors use a subtractive aluminum/chemical vapor deposition (CVD) oxide metallization to build one or more layers of metal. For the production of planarized film layers or microlenses, organic polymers such as polyimide or novolac materials are also used, or siloxane polymers may sometimes be used.

Organic polymers can be divided into two different groups according to their dielectric constant. Non-polar polymers contain molecules that have almost exclusively covalent bonds. Since the non-polar polymer is composed mainly of non-polar C-C bonds, its dielectric constant can be estimated using only density and chemical composition. Polar polymers do not have low loss, but they contain atoms of different electronegativity, causing an asymmetric charge distribution. Polar polymers therefore have a higher dielectric loss and a dielectric constant, depending on the frequency and temperature at which they are evaluated. Several organic polymers have been developed for the purpose of dielectric properties. However, due to the low thermal stability, softness of these layers and the incompatibility with conventional techniques developed for SiO ₂ based dielectrics, the applicability of the above layers is limited. For example, organic polymers cannot be subjected to chemical mechanical polishing (CMP) or dry etchback treatment without damaging the film layer.

Therefore, some recent focus has focused on dielectrics and optical materials based on silsesquioxane or siloxane (SSQ) or cerium oxide. For SSQ-based materials, sesquioxanes (decanes) are the basic unit. The sesquioxane or T resin (T-resin) is an organic-inorganic hybrid polymer having the experimental formula (R-SiO _3/2 ) _n . The most common representative of such materials includes a ladder structure, and the cage structure containing eight deuterium atoms (T ₈ cubes) placed at the apex of the cube may include hydrogen, alkyl, alkenyl. , alkoxy and aryl. Many sesquioxins have moderately good solubility in common organic solvents due to their organic substitution of Si. Organic substitutes provide a low density and low dielectric constant matrix material. The lower dielectric constant of the matrix material is also attributed to the low polarizability of the Si-R bond compared to the Si-O bond in SiO ₂ . The sesquioxane-based materials used in microelectronic applications are mainly hydrogen-silsesquioxane (HSQ) and methyl-silsesquioxane (MSQ) (CH ₃ -R-SiO _3/2 ) _n . MSQ materials due to the large size of the CH ₃ group and having a low dielectric constant compared with the HSQ of, respectively, about 2.8 and 3.0-3.2, Si-CH, and as compared with the Si-H bonds lower ₃ Polarization. However, the refractive index of such layers in the visible range is typically between about 1.4 and 1.5, and typically less than 1.6.

The material based on vermiculite ceria has a tetrahedral basic structure of SiO ₂ . 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 at the center of the regular tetrahedron of the oxygen atom, that is, it forms a bridging crosslink. All pure vermiculite ceria has a dense structure with high chemical stability and excellent thermal stability. For example, the amorphous vermiculite dioxide film used in microelectronics has a density of from 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 high polarization of the Si-O bond, the dielectric constant is also high, in the range of 4.0 to 4.2. Therefore, it is necessary to replace one or more Si-O-Si bridging groups with a C-containing organic group (such as a CH ₃ group) having a reduced k value. However, due to steric 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 chemical resistance are reduced as compared with tetrahedral cerium oxide. Again, such methyl-based silicates and SSQ (i.e., MSQ) polymers have relatively low rupture thresholds, typically about 1 μm or less.

It is an object of the present invention to provide a novel high refractive index siloxane polymer that is compatible with conventional integrated circuit (IC) processes and CMOS image sensor applications.

Another goal is to provide a method of modifying a monomer to form a novel organo-functionalized molecule.

A third object of the present invention is to provide a process for producing a poly(organosiloxane) composition suitable for the preparation of films having excellent dielectric properties as well as optical properties.

A fourth object of the present invention is to provide a novel film having a low dielectric constant, excellent mechanical properties, and thermal properties, which is formed of the above-mentioned polymer.

A fifth object of the invention is to provide a dielectric layer on germanium and on a glass wafer.

These and other objects that are readily apparent from the following description, along with their advantages over known dielectric films and methods for their preparation, are accomplished by the invention described and claimed hereinafter.

In order to achieve such objects in the present invention, a novel polyorganosilsesquioxane material based on a polydecane molecule and used as an interlayer insulating film for a semiconductor or photovoltaic device is introduced.

In general, the monomer of the novel material comprises: at least two metal atoms interconnected by a bridged hydrocarbon group and exhibiting hydrolyzable substituents on both metal atoms; together with at least one organic group, which is capable of reducing the extremes of the polymer The polymer is further crosslinked with a polymer to form a nano-sized porosity or a combination of all previous characteristics formed by the monomer.

In particular, the metal atom is a deuterium atom and the bridging group is a linear or branched (divalent) hydrocarbyl group to bond the two deuterium atoms together. Further, usually one of the ruthenium atoms contains three hydrolyzable groups, and the other ruthenium atom contains two hydrolyzable groups and an organic crosslinking group, a reactive cleavage group or a polarized reduced organic group ( Such as an alkyl, alkenyl, alkynyl, aryl, polycyclic group or organic containing silicon group. The latter group can also be fully or partially fluorinated.

The general formula I used in the precursor of the present invention is of the following formula: Wherein: R ₁ is a hydrolyzable group (such as hydrogen, halide, alkoxy or acyloxy group); R ₂ is hydrogen, an organic crosslinking group, a reactive cleavage group or a polarizability The organic group is reduced; and R ₃ is a bridged or branched divalent hydrocarbon group.

In the process of the invention, Formula I covers two slightly different types of precursors, i.e., corresponding to the first primary precursor of Formula I, wherein R ₂ represents hydrogen. The second species of precursor has the formula I, wherein R ₂ represents an organic crosslinking group, a reactive cleavage group, or a polarizing reduced organic group, or a combination thereof. Such groups are represented by alkyl, alkenyl, alkynyl, aryl, polycyclic groups and organic group-containing groups.

The compound according to the formula wherein the R ₂ group is hydrogen may be formed by a hydrosilylation reaction in which trihalosilane and dihalosilane are reacted in the presence of cobalt octacarbonyl. To form a 1,1,1,4,4-pentafluoro-1,4-dioxane (1,1,4,4-pentahalo-1,4-disilabutane) intermediate with good yield. This intermediate can be converted, for example, by hydrogenation of hydrazine to replace the hydrogen at position R ₂ such that an organofunctionalized decane is formed. If the R ₂ 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 a combination thereof.

The polymer of the present invention is further polymerized by hydrolyzing a hydrolyzable group of a polydecane monomer or a combination of the polymers described in the present invention or a combination of a molecule of the present invention with a molecule known in the art and subsequently by a condensation polymerization process. It comes to be produced.

New materials can be used, for example, as optical dielectric films in articles containing (矽) wafers.

The present invention also provides a method for forming a film having a dielectric constant of 4.0 or less (or preferably 3.5 or less) and a refractive index of greater than 1.58 (or preferably greater than 1.60) in the wavelength range of 632.8 nm, It comprises a monomer having Formula I to form a decane material, depositing a siloxane material in a thin layer and curing the thin layer to form a film layer.

A number of advantages are obtained from current novel materials and by methods of making them. Accordingly, the present invention proposes a solution to the existing problems associated with optical dielectric polymers. More specifically, the present invention proposes solutions to existing problems associated with refractive index, CMP compatibility, mechanical properties (modulus and hardness), crack thresholds, and thermal characteristics, as well as IC integrated body temperatures. In particular, the film layer is also suitable for enhanced curing of light or radiation (preferably ultraviolet (UV) wavelength or electron beam (e-beam)), which is carried out simultaneously with the heat curing process.

Novel organofunctional molecules can be constructed in such a form that they can react further in the matrix. This means that the organic function of the molecule can, for example, undergo cross-linking, splitting, or a combination of both (ie, subsequent splitting and cross-linking reactions).

The present invention provides excellent chemical resistance due to the density of highly crosslinked bridging groups and very low chemisorption properties.

If the R ₂ group is a split group, it still results in a very small pore size (i.e., usually 1.5 nm or less). However, the polymers formed according to the innovative invention are also compatible with conventional types of porogens such as cyclodextrin, which can be used to form micro-forms in polymers. The micro-porosity and thus the dielectric constant of the polymer.

Another important advantage is that the novel optical dielectric materials have excellent planarization characteristics that result in excellent locality and global flatness in the configuration of the semiconductor substrate, which reduces or even completely eliminates dielectric and oxide liners. The need for chemical mechanical planarization after pad deposition.

In addition, the new materials have excellent gap filling characteristics.

By incorporating nanoparticle into a material comprising a dioxane structure having a functional group as desired, it is possible to modify the higher refractive index of the refractive index (about less than 1.5) of a conventional azide material (about A refractive index of up to 1.75 or higher is obtained at about 1.65), which makes the new materials particularly suitable for CMOS camera applications.

In summary, the present invention provides an optical dielectric siloxane polymer suitable for forming a thermally stable and mechanically stable high refractive index dense dielectric film having a high fracture threshold, a low pore volume, and a pore size. The polymer, after undergoing heat treatment, will result in a non-aqueous, silanol-free film layer with excellent local flatness, global flatness, and gap filling, which has excellent electrical and optical properties. Film layers made from new polymers remain structurally, mechanically, and electrically unchanged after final curing, even when subjected to temperatures above the final cure temperature. Since all of these properties are superior to conventional optical dielectric polymers, they are critical to overcoming existing problems and improving device performance in the integration of optical dielectric films into optical semiconductor devices.

Next, the present invention will be examined more closely by means of the following embodiments and with reference to a number of working examples.

The present invention provides an optical dielectric polymer comprising at least one polydecane monomer unit having at least one organic bridging group between deuterium atoms. In addition, one of the germanium atoms also contains an organic crosslinking group, a reactive splitting group, a refractive index increasing group, a UV blocking group, a polarizing reducing organic group or a combination of all the foregoing (such as an alkane). A base, an alkenyl group, an alkynyl group, an aryl group, a polyaryl group, a polycyclic group or a group containing a fluorene group.

One of the ruthenium atoms contains two hydrolyzable groups, and the other contains three hydrolyzable groups which, upon hydrolysis and polymerization, are capable of forming a continuous siloxane base matrix, such as hydrogen, halides. Alkoxy or alkoxy, but most preferably a chlorine, methoxide or ethoxy group or any combination thereof.

The general formula I used for the pre-polymerization of the present invention is as follows: Wherein R ₁ is a hydrolyzable group; R ₂ is an organic crosslinking group, a reactive cleavage group, a polarizing reducing organic group or a combination of all the foregoing, such as an alkyl group, an alkenyl group, an alkynyl group, An aryl group, a polycyclic group or an organic group containing a group; and R ₃ is a bridged or branched divalent hydrocarbon group.

R _{1 is} preferably a group selected from the group consisting of a halide, an alkoxy group, a decyloxy group, and hydrogen, and R _{2 is} preferably selected from an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, a polycyclic group or a hydrazine-containing group. a group, and R _{3 is} preferably selected from linear and branched alkylene groups, alkenylene groups and alkynylene groups, and bivalent alicyclic groups (polycyclic groups) And a divalent aromatic group, which are all included in the definition of a divalent hydrocarbon group.

The cured composition obtained by substantially homopolymerizing a monomer of the above formula and subsequently cured to achieve crosslinking comprises a crosslinked organosiloxane polymer, that is, a poly(organosiloxane) which can be formed into a film. .

"Alkenyl" as used herein includes both straight-chain and branched alkenyl groups such as vinyl and propenyl. The term "alkynyl" as used herein includes both straight-chain and branched alkynyl groups (suitably acetylene). "Aryl" means a substituted, unsubstituted, mono-, bi- or more cyclic aromatic carbocyclic group; examples of aryl are phenyl, naphthyl or pentafluorophenyl propyl. As used herein, a "polycyclic" group includes adamantyl, dimethyl adamantly propyl, norbornyl or norbornene. More specifically, the alkyl, alkenyl or alkynyl group can be linear or branched.

The alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms. The alkyl group preferably branches at the α or β position, has one or more (preferably two) C ₁ to C ₆ alkyl groups, and is particularly 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, butan-2-yl, 2-methylbutan-2-yl, and 1,2-dimethylbut-2- base. In particular, the alkyl group is a lower alkyl group having 1 to 6 carbon atoms, which optionally has 1 to 3 substituents selected from a methyl group and a halogen. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl are especially preferred.

The alkenyl group preferably has 2 to 18 carbon atoms, more preferably 2 to 14 carbon atoms, and particularly preferably 2 to 12 carbon atoms. The group of ethylene (i.e., two carbon atoms bonded by a double bond) is preferably located at position 2 or higher, and is related to the Si atom in the molecule. The branched alkenyl group preferably branches at the α or β position, has one or more (preferably two) C ₁ to C ₆ alkyl, alkenyl or alkynyl groups, particularly preferably fluorinated or perfluorinated. Alkyl, alkenyl or alkynyl.

The alkynyl group preferably has 3 to 18 carbon atoms, more preferably 3 to 14 carbon atoms, and particularly preferably 3 to 12 carbon atoms. The ethynyl group (i.e., the two carbon atoms bonded by a triple bond) group is preferably located at position 2 or higher, and is related to the Si atom in the molecule. The branched alkynyl group preferably branches at the α or β position, having one or more (preferably two) C ₁ to C ₆ alkyl, alkenyl or alkynyl groups, particularly preferably a perfluorinated alkyl group, Alkenyl or alkynyl.

The divalent alicyclic group may be a polycyclic aliphatic group including a residue derived from a cyclic structure having 5 to 20 carbon atoms, such as norbornene (nortenyl group) and adamantyl group (amantane) (adamantylene)). "Arylene" means a divalent aryl group containing from 1 to 6 rings, preferably 1 to 6 fused rings, and in detail 1 to 5 fused rings, such as benzene. Base, anthranyl and anthracenyl).

The aryl group is preferably a phenyl group which optionally has 1 to 5 substituents selected from a halogen, an alkyl group or an alkenyl group on the ring; or a naphthyl group which optionally has a halogen group or an alkyl group selected from the ring structure. From 1 to 11 substituents of a base or alkenyl group, the substituents are optionally fluorinated (including perfluorinated or partially fluorinated).

The polycyclic group is, for example, adamantyl, dimethyldetylpropyl, norbornyl or norbornene, which may optionally have from 1 to 8 substituents or, if desired, from 1 to 12 carbons. The base, alkenyl, alkynyl or aryl group is separated from the ruthenium atom.

"Hydrolyzable group" represents halogen (chloro, fluoro, bromo), alkoxy (detailed C _1-10 alkoxy such as methoxy, ethoxy, propoxy or butoxy), hydrazine Oxygen, hydrogen or any other group that can be easily split away from the monomer during polymerization (eg, condensation polymerization).

Alkoxy usually represents a group of the formula R ₄ O- wherein R ₄ as defined above represents an alkyl group. The alkyl residue of the alkoxy group can be linear or branched. Typically, the alkoxy group contains a lower alkoxy group having from 1 to 6 carbon atoms (such as a methoxy group, an ethoxy group, and a third butoxy group).

The decyloxy group has the formula R ₅ O ₂ -, wherein R _{5 is} as defined above to represent an alkyl group. In particular, the alkyl residue of the methoxy group may have the same meaning as the corresponding residue in the alkoxy group.

In the context of the disclosure, the organic group substituent halogen can be an F, Cl, Br or I atom and is preferably F or Cl. Generally, the term "halogen" as used herein means a fluorine, chlorine, bromine or iodine atom.

In the monomer of formula I, the germanium atoms are bonded to each other via a linker group. Typically, the linking agent comprises from 1 to 20 (preferably from about 1 to about 10) carbon atoms. Examples of suitable linking group R ₃ include alkylene, alkenylene and alkynylene. "Alkylene" group generally having the formula - (CH _{2) r} -, wherein r is an integer of from 1 to 10. One or both of the hydrogen of at least one unit -CH ₂ - may be substituted by any of the substituents mentioned below. An "alkenylene" group corresponds to an alkylene residue containing at least one double bond in the hydrocarbon backbone. If several double bonds are present, they are preferably conjugated. In contrast, an "alkynylene" group contains at least one triple bond in the hydrocarbon backbone corresponding to an alkylene residue.

The divalent linking agent residue can be unsubstituted or substituted. The substituent is preferably selected from the group consisting of a fluoro group, a bromo group, a C _1-10 alkyl group, a C _1-10 alkenyl group, a C _6-18 aryl group, an acryl group, an epoxy group, a carboxyl group, and a carbonyl group. A particularly interesting alternative comprises a methylene group substituted with at least one alkyl group, preferably a lower alkyl group or from 1 to 4 carbon atoms. As a result of the substitution, a branching linker chain is obtained. Branched chain linking agents (e.g., -CH (CH ₃₎ -) may contain the entire (e.g., -CH ₂ CH ₂ -) and a corresponding plurality of carbon atoms as the linear, even if some of the carbon atoms located in a branched chain, as described below in conjunction with The work example is shown. For the purposes of the present invention, such molecules may be considered "isomeric."

As an example of a particularly preferred compound according to formula I, mention may be made of 1-(trichlorosilyl)-2-(methyldichlorosilyl)ethane (1-(trichlorosilyl)-2-(methyldichlorosilyl)ethane) And 1-(methyldichlorosilyl)-1-(trichlorosilyl)ethane.

As mentioned above, in the first step of the process according to the invention, a monomer having the formula: Wherein R ₁ is a hydrolyzable group; R ₂ is hydrogen; and R ₃ is a bridged or branched divalent hydrocarbon group.

This monomer and a similar decane-based material can be produced by a hydrogenation reaction of hydrazine, and the hydrazine hydrogenation reaction is carried out under the condition that cobalt octacarbonyl is used as a catalyst.

In particular, the novel hydrazine hydrogenation catalyzed in the presence of cobalt octacarbonyl or typically any transition metal octate catalyst, uses halodecane as the reactant. Therefore, in order to produce a compound of the above formula (wherein R ₂ represents hydrogen) in a high yield, the first trihalodecane compound may be reacted with the second dihalogenated nonane compound in the presence of cobalt octacarbonyl. The trihalodecane used typically has a reactive organic group containing an unsaturated bond to aid in the rhodium hydrogenation reaction.

This reaction is illustrated below in Example 1, wherein vinyl trichloromethane is reacted with dichlorosilane to form 1,1,1,4,4-pentachloro-1,4-dioxane.

Surprisingly, by the disclosed method, the desired compound of high purity is obtained, which allows the subsequent step of preparing the oxoxane material by incorporation of the desired substituent at the R ₂ position, using the monomer as a precursor .

The present invention provides an optical dielectric siloxane polymer suitable for forming thermally stable and mechanically stable, high refractive index, optically clear, high cracking threshold, dense and low pore volume, and pore size dielectric films. The polymer, after being subjected to a heat treatment, produces a film of water-free and stanol having excellent local and global flatness and gap filling, which has excellent electrical properties. Films made from the inventive polymers remain structurally, mechanically, and electrically unchanged after final curing, even when subjected to temperatures above the final cure temperature. Since all of these characteristics are superior to conventional low dielectric constant polymers, they are critical to overcome the existing problems of integrating low dielectric constant films into semiconductor devices.

Polymerization synthesis is based on hydrolysis and condensation chemical synthesis techniques. The polymerization can be carried out in the 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 200 ° C, usually from about 25 ° C to about 160 ° C, in particular from about 80 ° C to about 150 ° C. Typically, the polymerization is carried out under ambient pressure and the maximum temperature is set by the boiling point of any solvent used. The polymerization can be carried out under reflux conditions. It is possible to polymerize an instant monomer without a catalyst or by using a basic (or in particular acidic) catalyst.

Current organooxane materials have a (weight average) molecular weight of from 500 to 100,000 g/mol. The molecular weight may be below the lower end of the range (for example, from 500 to 10,000 g/mol or more preferably from 500 to 8,000 g/mol) or the organodecane material may have an upper end of the range (please, for example, from 10,000 to 100,000 g/ The molecular weight of mol or better from 15,000 to 50,000 g/mol). It may be desirable to mix a polymeric organic siloxane with a lower molecular weight and an organic siloxane having a higher molecular weight.

Suitable polymer compositions have been found to be obtainable by homopolymerizing a monomer of formula I comprising a linear or branched linkage group. However, a first monomer having a formula I (wherein R ₃ represents a linear divalent hydrocarbon residue) and a second monomer having a formula I (wherein R ₃ represents a branched divalent hydrocarbon residue) are provided. It is also possible to obtain a composition having a molar ratio of the first monomer to the second monomer of from 95:5 to 5:95, in particular from 90:10 to 10:90, preferably from 80:20 to 20: 80. In addition, the monomer of formula I may also be in any ratio with any known hydrolyzable oxirane or organometallic (eg, titanium alkoxide, titanium chloride, zirconium alkoxide, zirconium chloride, A monomeric copolymer of tantalum alkoxide, cerium chloride, aluminum alkoxide or aluminum chloride (but not limited thereto).

According to a preferred embodiment, the germanium oxide material deposited on the substrate of the semiconductor device is heated to cause further crosslinking for the purpose of modifying the properties, thereby obtaining less than 10%, preferably less than 5% after heating, in detail A film layer having a shrinkage of less than 2% and a thermal stability exceeding 425 °C.

According to a particular embodiment, the film layer is baked after spin coating at a temperature below about 200 ° C and then exposed to UV radiation by heat treatment at a temperature below 450 ° C for 0.1 to 20 minutes. Cured. Curing is carried out for a sufficient period of time to react the organic substituent at the position R ₂ by the unit derived from the monomer of formula I above.

The polymer of the present invention can form a dielectric constant of 4.0 or less (detailed 3.5 or less) after being subjected to heat treatment, and has a density of 1.58 or more in the wavelength range of 632.8 nm (specifically 1.60 or more). The refractive index has a Young's modulus of 5.0 Gpa or more, a porosity of 5% or less, and a low dielectric film having a fracture threshold of 1 μm or more. Further, the film layer formed of the polymer using the polydecane component remains stable on the semiconductor structure at a temperature of up to 400 ° C or higher.

The oxoalkyl group can be doped with nanoparticle for further modification. Such nanoparticles include oxides, semiconductors, and metal nanoparticles. It is advantageous to chemically dope the oxyalkylene with nanoparticle to modify or modify the properties of the siloxane polymer, such as optical, electrical, and mechanical properties. Nanoparticles can be modified by coupling chemical groups on the surface of the nanoparticles. These chemical coupling groups are usually so-called silane-coupling groups, but are not limited to them. The decane coupling element is, for example, amino propyl trimethoxysilane, methacryloxy propyl trimethoxysilane or glycidoxy propyl trimethoxysilane. And other similar groups having a decane 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 oxoalkyl group and also enables the particle to be covalently bonded to the oxoalkyl group. The number of coupling elements can also vary at the surface of the nanoparticle. The relative amount of the linking agent can be 1 or higher, and typically has more than one linking agent molecule on the surface to ensure adequate bonding to the polymer matrix is preferred.

Typically, the polymer or copolymer is incorporated in an amount of 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 and 100 parts by weight of the polymer or copolymer. To form a composition containing nanoparticles.

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 polymers or copolymers with nanoparticles in such a way that some bonds (preferably chemical bonds) are formed between the polymer or copolymer and the nanoparticles. Therefore, it is possible to use a polymer or copolymer having a reactive group capable of reacting with nanoparticles and forming a bond between the polymer or copolymer and the nanoparticles. It is also possible to use nanoparticles having a decane coupling element or group as discussed above. The physical bonding between the constituents will also enhance the mechanical, optical and electrical properties of the composition.

One embodiment comprises the use of chemically bonded nanoparticles and mixtures of different polymers, wherein the mixture of different polymers comprises an ordered copolymer. The nanoparticles are bonded to at least one polymer component of the mixture.

Suitable for fabrication by, for example, a method selected from the group consisting of alkaline solutions or acidic solution chemistry, flame hydrolysis, laser densification, and a combination of two or more of these methods Nanoparticles for use in the present invention. However, this list in no way limits the scope of the invention, any method that will result in particles having the desired particle size can be used. Particle size (average particle size) can range from 1 nm to several microns, and particle sizes typically 20 nm or less (more about 0.5 nm to about 18 nm) in optical and IC applications are preferred. . Further, it is preferable that the particle size distribution range is narrow, but it is not essential.

Typical materials to be doped to the 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.

Metal oxides: TiO ₂ , ZnO, Ta ₂ O ₅ , Nb ₂ O ₅ , SnO ₂ , ZrO ₂ , MgO ₂ , Er ₂ O ₃ and SiO ₂ .

Carbide: SiC.

Nitride: Si ₃ N ₄ , AlN, and TiN.

Suitable nanoparticle materials are discussed in U.S. Patent Application Serial No. 2005/0170192, the disclosure of which is incorporated herein by reference.

Nanoparticles are usually used in the form of dispersions ("dispersions"). Suitable dispersing agents include water, organic solvents such as alcohols and hydrocarbons, and combinations and mixtures thereof. The choice of preferred solvent will generally depend on the characteristics of the nanoparticles. Therefore, the dispersant and the nanoparticles should be selected to be compatible with the requirements for forming well dispersed particles. For example, although the preferred pH depends on the crystal structure and surface structure, gamma alumina particles are generally well dispersed at an acidic pH of about 3-4, and the cerium oxide particles are usually at an alkaline pH. The value is easily dispersed in the case of 9-11, and the titanium oxide particles are usually well dispersed at a pH close to 7. Generally, nanoparticles having a small surface charge can be preferentially dispersed in a less polar solvent. Therefore, the hydrophobic particles can be dispersed in a non-aqueous (anhydrous) solvent or an aqueous solution having a less polar cosolvent, and the hydrophilic particles can be dispersed in an aqueous solvent.

In such nanoparticle solvent dispersions, the surface of the particles may also be treated with a decane coupling agent. The hydrolyzable moiety of these coupling groups spontaneously reacts with the surface of the nanoparticles, especially in the presence of water as a hydrolysis catalyst.

As mentioned above, the present invention also provides a method of fabricating an integrated circuit device. The methods generally include the steps of: forming a plurality of transistors on a semiconductor substrate; forming a plurality of interconnects by: depositing a metal layer; patterning the metal layer; depositing the first modulus and the first k value a first dielectric material; depositing a second dielectric material having a second modulus higher than a first modulus of the first material and having a k value lower than a first k value of the first material; and patterning the first A dielectric material and a second dielectric material are deposited and a via fill metal material is deposited in the patterned region.

The material for the first dielectric layer according to the present invention is preferably an organic siloxane material having a repeating -M-O-M-O-backbone having a first organic substituent bonded to the main chain, the material It has a molecular weight of from 500 g/mol to 100,000 g/mol, wherein M is hydrazine and O is oxygen. The molecular weight is from 1500 g/mol to 30,000 g/mol, and it preferably exhibits one or several of the following characteristics: a k value of 4.0 or less, or more preferably 3.5 or less; a refractive index of 1.58 or more, More preferably, it is 1.6 or more; a coefficient of thermal expansion (CTE) of 30 ppm or less; and a Young's modulus of 4 GPa or more.

Due to the excellent properties of planarization, the patterning step can be performed without the previous steps of chemical mechanical planarization. Alternatively, 45% or less of the total thickness of the second dielectric material is removed by performing chemical mechanical planarization on the second dielectric material.

The organooxane material can be deposited as a thin layer and a cured thin layer by polymerizing a monomer of formula I in a liquid medium formed from a first solvent to form a hydrolysate comprising a oxoxane material. It is deposited by forming a film having a thickness of 0.01 μm to 10 μm.

Alternatively, the organooxane material can be polymerized with a monomer of formula I and any known hydrolyzable siloxane or organometallic (eg, titanium alkoxide, titanium chloride, in a liquid medium formed from the first solvent). a zirconium alkoxide, zirconium chloride, cerium alkoxide, cerium chloride, aluminum alkoxide or aluminum chloride (but not limited thereto) monomer to form a cerium-containing material or a mixed cerium-oxygen metal material. The hydrolyzate is deposited on the substrate as a thin layer and the thin layer is cured to form a film having a thickness of 0.01 μm to 10 μm.

In view of the fact that one of the dielectric materials comprises a material according to the invention, the other material may be a known organic, inorganic or organic/inorganic material, such as the ones discussed above in the introductory part.

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 30 ppm. It may have a refractive index of 1.6 or less.

Additional details of the invention can be discussed in conjunction with the following working examples:

Instance Example 1

1,1,1,4,4-pentachloro-1,4-dioxane (intermediate)

Ethylene trichloromethane (68.8 g, 426 mmol) and cobalt octacarbonyl (700 mg) were placed in a 100 mL rb flask and cooled to 0 ° C in an ice bath. Dichlorodecane (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. Distillation at 60 ° C / 8 mbar to 62 ° C / 8 mbar, while giving 1,1,1,4,4-pentachloro-1,4-dioxane (120.8 g, 460 mmol) in 93% yield ).

Example 2

Tris(3,3,6,6-pentachloro-3,6-dihexyl)chlorosilane (tris(3,3,6,6,6-pentachloro-3,6-disilahexy)chlorosilane)

11.00 g (0.076 mol) of trivinylchloromethane was added to a 100 ml vessel followed by 2 ml of 1,1,1,4,4-pentachloro-1,4-dioxane. The solution was heated to 80 ° C and 15 μL of a 10% H ₂ PtCl ₆ /IPA solution was added. A strong exothermic reaction was observed and the heating source was turned off. The remaining 1,1,1,4,4-pentachloro-1,4-dioxane was slowly added over a period of 30 minutes while maintaining the temperature of the solution below 130 °C. The total amount of 1,1,1,4,4-pentachloro-1,4-dioxane was 61.50 g (0.234 mol, 2.6% excess). After the addition, the heating source was turned on again, and the solution was stirred at 110 ° C for one hour. Thereafter, the solution was distilled to obtain 47.08 g (66%) of tris(3,3,6,6,6-pentachloro-3,6-dihexyl)chlorodecane. Bp264 ° C / < 0.5 mbar.

Example 3

1,1,1,4,4,7,7,7-octachloro-1,4,7-triheptane (1,1,1,4,4,7,7,7-octachloro-1, 4,7-trisilaheptane)

Ethylene trichloromethane (16.8 g, 104 mmol) was heated to 60 ° C and 100 μL of a 10% H ₂ PtCl ₆ /IPA solution was added. 1,1,1,4,4-pentachloro-1,4-dioxane (20.4 g, 77.7 mmol) was slowly added during 20 minutes so that the temperature did not exceed 100 °C. The reaction was allowed to proceed at 100 ° C for 12 hours, 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-octachloro-1,4,7-trioxane (1,1,1,4,4,7,7,7-octachloro-1, 4,7-trisilaoctane)

1,1,1,4,4-pentachloro-1,4-dioxane (51.6 g, 196 mmol) was heated to 80 ° C and 20 μL of a 10% H ₂ PtCl ₆ /IPA solution was added. Ethylene methyl dichloromethane (29.7 g, 210 mmol) was slowly added during 20 minutes so that the temperature did not exceed 130 °C. The reaction was allowed to proceed for 1.5 hours, after which it was distilled under vacuum at 90-102 ° C / < 1 mbar. The yield was 70.2 g (174 mmol, 89%).

Examples 5 to 7

1,1,1,4,4-pentachloro-1,4-dioxane (1,1,1,4,4-pentachloro-1,4-disiladecane) 1,1,1,4,4- Pentachloro-1,4-dioxane (1,1,1,4,4-pentachloro-1,4-disiladodecane) 1,1,1,4,4-pentachloro-1,4-dioxene Tetradecane (1,1,1,4,4-pentachloro-1,4-disilatetrakaidecane)

32 ml (21.53 g, 0.256 mol) of 1-hexene and 20 μL of H ₂ PtCl ₆ /IPA solution were added to a 100 ml container. The solution was heated to 80 ° C and 46.90 g (0.179 mol) of 1,1,1,4,4-pentachloro-1,4-dioxane was slowly added over a period of 30 minutes. When an exothermic reaction is observed, the heat source is turned off. The temperature during the addition was kept below 130 °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 was purified by distillation. Bp100 ° C / 0.8 mbar. The yield was 50.40 g (81.4%). 1-hexene can be replaced by 1-octene or 1-decene to produce 1,1,1,4,4-pentachloro-1,4-dioxane, respectively (bp 131 ° C / 0.7 mbar, 88% Yield) and 1,1,1,4,4-pentachloro-1,4-dioxanetetradecane (bp 138 ° C / 0.8 mbar, 82% yield).

Example 8

1,1,1,4,4-pentachloro-7-phenyl-1,4-dioxane (1,1,1,4,4-pentachloro-7-phenyl-1,4-disilaheptane)

18.77 g (0.159 mol) of allylbenzene and 50 μL of H ₂ PtCl ₆ /IPA solution were added to a 100 ml container. The solution was heated to 80 ° C and 41.85 g (0.159 mol) of 1,1,1,4,4-pentachloro-1,4-dioxane was slowly added over a period of 30 minutes. When the exothermic reaction is observed, the heat source is turned off. The temperature during the addition was kept below 130 °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 was purified by distillation. Bp 137 ° C / 0.8 mbar. The yield was 35.10 g (58%).

Example 9

1,1,1,4,4-pentachloro-6-pentafluorophenyl-1,4-dioxane (1,1,1,4,4-pentachloro-6-pentafluorophenyl-1,4-disilahexane )

116.15 g (0.442 mol) 1,1,1,4,4-pentachloro-1,4-dioxane was added to a 250 ml vessel, followed by the addition of 100 μL of H ₂ PtCl ₆ /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-1,4-dioxin-5-hexene (1,1,1,4,4-pentachloro-1,4-disila-5-hexene)

40.00 g (0.152 mol) 1,1,1,4,4-pentachloro-1,4-dioxane dissolved in 1000 ml of 1,4-dioxane in a 2000 ml vessel (1,4- Dioxane). The solution was cooled to 0 ° C and acetylene was poured into the solution to foam until it was saturated. The solution thus obtained is slowly heated to room temperature. The 1,4-dioxane was evaporated and the crude 1,1,1,4,4-pentachloro-1,4-diox-5-hexene obtained was reduced by distillation.

Example 11

1,1,1,4,4-pentachloro-7-(3,5-dimethyladamantyl)-1,4-dioxane (1,1,1,4,4-pentachloro-7 -(3,5-dimethyladamantyl)-1,4-disilaheptane)

81.71 g (0.336 mol) of 3,5-dimethyladamantlybromide was dissolved in 500 ml of pentane. The solution was cooled from ice/acetone bath to below -10 °C. Was added 51.40 g (0.425 mol) of allyl bromide (allylbromide), followed by addition of 410 mg of FeBr _3. 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), and the results showed that some unreacted raw materials remained. 420 mg of FeBr _{3 was added} and the solution was stirred for an additional two hours, after which the results of GC-MS showed that all of the dimethyldane-alkyl bromide had reacted. The solution was warmed to room temperature and rinsed twice with 500 ml of water. The organic layer was collected and the pentane was evaporated. The remaining material was dissolved in 700 ml of ethanol and a small amount of water was added followed by 25 g (0.382 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. 300 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 filtered. The pentane was evaporated and the crude 1-allyl-3,5-dimethyladamantane was purified by distillation to yield 45.90 g (67%). 1-Allyl-3,5-dimethyladamantane was transferred to a 100 ml vessel followed by 50 μL of H ₂ PtCl ₆ /IPA solution. The solution was heated to 85 ° C and 59.50 g (0.227 mol) of 1,1,1,4,4-pentachloro-1,4-dioxane was slowly added over 30 minutes. After the addition, the solution was heated to 100 ° C and stirred for one hour. The product thus obtained was then purified by distillation to give a yield of 53.54 g (51%), bp. 157-158 ° C / < 0.5 mbar.

Example 12

1,1,1,4,4-pentachloro-5,6-dimethyl-1,4-dioxin-6-heptene (1,1,1,4,4-pentachloro-5,6-dimethyl -1,4-disila-6-heptene)

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) Palladium (0) (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 stirred at 100 ° C 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 H ₂ PtCl ₆ /IPA catalyst at 80 ° C or with a Co ₂ (CO) ₈ catalyst at room temperature, a 1:1 mixture of α and β substituted isomers is obtained.

Example 13

1,1,1,4,4-pentachloro-6-(5-norborn-2-ene)-1,4-dioxane (1,1,1,4,4-pentachloro-6-( 5-norborn-2-ene)-1,4-disilahexane)

22.63 g (0.086 mol) of 1,1,1,4,4-pentachloro-1,4-dioxane was added to a 100 ml vessel, followed by the addition of 70 μL of H ₂ PtCl ₆ /IPA solution. The obtained solution was heated to 85 ° C, and then 10.81 g (0.090 mol) of 5-vinyl-2-norbornene was slowly added during 30 minutes. After the addition, the solution was stirred at 100 ° C for one hour and then distilled. Bp. 140 ° C / < 1 mbar, yield 20.05 g (61%).

Example 14

9-phenanthrenyl triethoxysilane

5.33 g (0.219 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. 196 ml (182.74 g, 0.877 mol) of Si(OEt) ₄ was added to the vessel. 200 ml of THF was added, and an exothermic reaction occurred after that. After the solution had cooled, it was heated to reflux and stirred overnight.

The reflux was stopped and 300 ml of n-heptane was added. The solution was poured into another container and the remaining solid was rinsed twice with 200 ml of n-heptane. A rinsing solution is added to the reaction solution. THF and n-heptane were evaporated and the remaining material was distilled. B.p. 175 ° C / 0.7 mbar. The yield was 52.63 g = 70%.

Example 15

1-(9-phenanthryl)-1,1,4,4,4-pentamethoxy-1,4-dioxane (1-(9-phenanthrenyl)-1,1,4,4,4 -pentamethoxy-1,4-disilabutane)

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 mol) was added to the vessel followed by 200 ml of THF. An exothermic reaction occurs within a few minutes. After the solution had cooled, it was heated to reflux and stirred overnight.

The reflux was stopped and 300 ml of n-heptane was added. The solution was poured into another container and the remaining solid was rinsed twice with 200 ml of n-heptane. A rinsing solution is added to the reaction solution. THF and n-heptane were evaporated and the remaining material was distilled. B.p. 190-205 ° C / < 0.1 mbar. The yield was 59.23 g = 65%.

Example 16

3-(9-phenanthrenyl)propyl trimethoxysilane

6.90 g (0.284 mol) of magnesium powder and a small amount of iodine crystals were added to a 1000 ml vessel, followed by the addition of 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 cooled back to room temperature, 30 ml of THF was added and the solution was heated to 65 ° C and stirred overnight.

The solution was allowed to cool to 50 ° C and 34.42 g (0.285 mol) of allyl bromide was added dropwise over 30 minutes at a rate to keep the solution gradually refluxed. After the addition, the solution was stirred at 65 ° C for 2 hours. The solution was cooled to room temperature and most of the THF was removed by vacuum. 700 ml of DCM was added and the solution was moved to a separation funnel. Rinse the solution twice with 700 ml of water. The organic layer was collected and dried over anhydrous magnesium sulfate. The solution was filtered and the solvent was evaporated. The remaining material was purified by distillation. B.p. 110-115 ° C / < 0.5 mbar. The yield was 54.5 g (88%).

Allylphenanthrene (41.59 g, 0.191 mol) was added to a 250 ml round bottom flask and heated to 90 °C. 50 μL of 10% H ₂ PtCl ₆ /IPA was added. The addition of HSiCl _{3 was} started and the exothermic reaction was observed. 26.59 g (0.196 mol) of HSiCl ₃ was slowly added during 40 minutes. After the addition, the solution was stirred at 100 ° C for one hour. Excess HSiCl _{3 was} removed by vacuum, and 100 ml (97 g, 0.914 mol) of trimethyl orthoformate was added, followed by the addition of 50 mg of Bu ₄ PCl as a catalyst. The solution was stirred at 70 ° C for 90 hours and the product was purified by distillation. Bp172 ° C / < 0.5 mbar. The yield was 50 g (74% based on the amount of allyl phenanthrene).

Example 17

High refractive index polymer 19-phenanthryl triethoxy decane (15 g, 44 mmol), acetone (22.5 g), and 0.01 M HCl (7.2 g, 400 mmol) were placed in a 100 mL rb flask, and Reflux for 23 hours. The volatiles were evaporated under reduced pressure. A white solid polymer (11.84 g) was obtained. The polymer was diluted in PGMEA (29.6 g, 250%) and subsequently cast on a tantalum wafer. Soft bake at 150 ° C for 5 minutes, followed by curing at 400 ° C for 15 minutes. The refractive index is 1.6680 in the wavelength range of 632.8 nm and the dielectric constant is 3.5 at 1 MHz. However, polymers do not have excellent chemical resistance relative to standard organic solvents and alkaline wet etch chemistries.

Example 18

High refractive index polymer 2 9-phenanthryl triethoxy decane (17.00 g, 0.05 mol from the Grignard reaction between 9-bromophenanthrene, magnesium and tetraethoxynonane in THF Prepared) and acetone (15.00 g) were stirred until the solids dissolved. Diluted nitric acid (0.01 M HNO ₃ , 6.77 g, 0.38 mol) was then added. The two phases (aqueous phase and organic phase) are separated. The system was refluxed until the solution became clear (about 15 minutes). Glycidyloxypropyitrimethoxysilane (3.00 g, 0.01 mol) was added and the flask was refluxed for six hours. The volatiles were evaporated in a rotary evaporator until 25.00 g of polymer solution remained. N-propyl acetate (32.50 g) was added and evaporation continued again until 27 g remained. Next, propylene glycol monomethyl ether acetate (PGMEA) (30 g) was added and evaporated again 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 50%. The solution was heated in an oil bath (165 ° C) and refluxed for 4 hours and 20 minutes. The water formed during the reaction was removed with the PGMEA in a rotary evaporator until 18 g remained. More PGMEA (42 g) was added to give the solution a solids content of 22.16%. The polymer had M _n /M _w =1,953/2,080 g/mol, and the above results were measured by glycidyloxypropyltrimethoxysilane (GPC) relative to monodisperse polystyrene standards in THF.

Sample preparation: The above solution (9.67 g) was formulated with PGMEA (5.33 g), a surfactant (BYK-307 from BYK-Chemie, 4 mg) and a cationic initiator (Rhodorsil 2074, 10 mg). It was spin-coated on a 4" wafer at 2,000 rpm. The film was soft baked at 130 ° C for 5 minutes and cured at 200 ° C for 5 minutes. The film thickness after curing was 310 nm and the refractive index was 632.8. The nm is 1.66 and the dielectric constant is 3.4 at 1 MHz. The film does not dissolve in acetone, which shows cross-linking has been successful. Similarly, the more concentrated PGMEA solution (solid 25%) It was prepared, spin coated and cured. The film layer was 830 nm thick and had a modulus of 7.01 Gpa and a hardness of 0.41 GPa as measured by nanoindentation.

Example 19

High refractive index polymer 3 1-(9-phenanthryl)-1,1,4,4,4-pentamethoxy-1,4-dioxane (9.55 g, 22.9 mmol), 9-phenanthryl Triethoxydecane (9.02 g, 26.5 mmol) 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 HCl (3.7 w-%) were added dropwise. Within two minutes, the solution became homogeneous, which showed the progress of hydrolysis. A solution of 1-(9-phenanthryl)-1,1,4,4,4-pentamethoxy-1,4-dioxane (11.45 g, 27.5 mmol) dissolved in acetone (16.0 g) was injected. Then, 0.01 M HCl solution (8.4 g, 466 mmol) was added. The reaction was allowed to reflux for 14 hours. After refluxing, all volatiles were removed under vacuum to give 28.1 g of dry polymer as a clear, colorless solid. It was characterized by thermogravimetric analysis (TGA) which was thermally stable up to 500 ° C in argon (Figure 2).

Solid in n-butyl acetate (NBA) (73.06 g, 260%) and surfactant (56 mg, Byk-Chemle BYK) Dilute in -307). Alternatively, a solution of propylene glycol monomethyl ether acetate (PGMEA, 240%) and methyl ethyl ketone (MEK, 400%) is also prepared. The NBA solution was filtered through a 0.2 μ Teflon filter and spun at 4 rpm on a 4" 矽 wafer at 3000 rpm. Soft bake at 150 ° C for 5 minutes and soft bake at 200 ° C for 5 minutes, followed by Curing at 400 ° C for 15 minutes in an N ₂ environment 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 layer is 3.4 at 1 MHz. The final thickness is up to 1850 nm. The film layer is prepared and does not exhibit cracking characteristics. The film layer can be rubbed against an organic solvent such as acetone without being damaged.

Example 20

High refractive index polymer 4 3-(9-phenanthryl)propyltrimethoxydecane (11.0 g, 32.4 mmol), acetone (16.5 g) and 0.01 M HCl were placed in a 100 ml rb flask and refluxed 16 hour. Initially, the solution was milky white, but became clear shortly after the start of hydrolysis. When the polymerization proceeded further, the solution became slightly turbid again. The volatiles were removed by evaporation under reduced pressure to give a white colourless powder, 9.60 g. The polymer was stable under argon at 450 ° C by TGA measurement (Figure 3).

The casting solution was obtained by 8.24 g of methyl ethyl ketone (400%) and a surfactant (5 mg, Byk-Chemie BYK) Prepared by dissolving 2.06 g of polymer in -307) and filtering through a 0.2 μ Teflon filter. 3000 rpm the polymer is cast on a rotating speed of 4 "silicon wafer. In soft baked at 150 deg.] C for 5 minutes and then cured at 400 deg.] C in an N ₂ environment for 15 minutes to obtain 632.8 nm 1.671 refraction of having Rate and thickness of 840 nm. The dielectric constant of the film is 3.4 at 1 MHz. The film does not exhibit cracking characteristics. The film can be rubbed against organic solvents such as acetone without damage.

Example 21

High refractive index polymer 5 9-phenanthryl triethoxy decane (17.00 g, 0.05 mol, prepared by the Grignard reaction between 9-bromophenanthrene, magnesium and tetraethoxynonane in THF) and acetone (15.00 g) was stirred until the solid dissolved. Diluted nitric acid (0.01 M HNO ₃ , 6.77 g, 0.38 mol) was then added. The two phases (aqueous phase and organic phase) are separated. The system was refluxed until the solution became clear (about 15 minutes). Glycidoxypropyltrimethoxydecane (3.00 g, 0.01 mol) was added and the flask was refluxed for six hours. The volatiles were evaporated in a rotary evaporator until 25.00 g of polymer solution remained. N-propyl acetate (32.50 g) was added and evaporation continued again until 27 g remained. Next, propylene glycol monomethyl ether acetate (30 g) was added and evaporated again 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 50%. The solution was heated in an oil bath (165 ° C) and refluxed for 4 hours and 20 minutes. The water formed during the reaction was removed with the PGMEA in a rotary evaporator until 18 g remained. More PGMEA (42 g) was added to give the solution a solids content of 22.16%. The polymer had M _n /M _w =1,953/2,080 g/mol, and the above results were measured by GPC relative to the monodisperse polystyrene standard in THF.

A 14% solution of PGMEA was prepared and a curing catalyst (0.3% from Rhodorsil 2074 from Rhodia) and a surfactant (0.2% from BYK307 from BYK-Chemie) were added. The material was spin coated onto a tantalum wafer and cured at 200 ° C for 5 minutes. The film layer can be cleaned with acetone without damage and it shows successful cure. It can be seen from Fourier transform infrared spectroscopy (FTIR) that the amount of stanol in the film layer is very low (a wide peak at 3200 cm ^-1 to 3800 cm ^-1 ).

If a curing catalyst is not used, the film will not cure and will be washed away by acetone. Also, the peak value of stanol in FTIR is high.

Example 22

Preparation of the polymer mixture of nanoparticles of TiO ₂ and polymer 5 rutile (Rutile) concentrate of 5 nm and rutile TiO ₂ particles (trade name from the NanoGram 'nSol-101-5K', 5% solution Formulated in MEK) to change the polymer/particle mass ratio from 3/1 to 1/3. A surfactant (BYK-307 from BYK-Chemie, 0.2%) and a cationic initiator (Rhodorsil 2074, 0.3%) were added to each sample. It was spin-coated on a 4" wafer at 2000 rpm. The film was soft baked at 130 ° C for 5 minutes and cured at 200 ° C for 5 minutes. The film thickness (Tx) and refractive index are summarized in Table 1. RI), and a reference sample diluted with PGMEA to form a film layer having a thickness of about 400 nm.

As can be seen from Table 1, the RI of the material increases as the loading of TiO ₂ increases. It can also be seen that the shrinkage rate does not change significantly.

Example 23

Preparation of a mixture of polymer 3 and rutile TiO ₂ nanoparticles The polymer 3 solution (in 17% dissolved in MEK) in the weight ratio of 1-2 was the same as the 5% TiO ₂ solution in Example 22. mixing. The solution was evaporated back to a solids content of about 17%. The solution was spin coated at 2000 rpm, followed by soft bake at 150 + 200 ° C for 5 + 5 minutes and at 300 ° C for 15 minutes. The results are shown in Table 2.

As can be seen, at a ratio of polymer to rutile TiO ₂ nanoparticles of 1-2, the refractive index of the film layer is increased by 0.2 units.

Example 24

Preparation of a mixture of polymer 5 and anatase TiO ₂ nanoparticles Polymer 5 in solid ratios 1-1 and 1-3 with anatase TiO2 nanoparticles (from Sumitomo's trade name 'ZRM-001 ', dissolved in MEK with 12%). The film was baked at 200 ° C for 5 minutes. The results are listed in Table 3.

As can be seen in Table 3, the refractive index of the film layer increases as the loading of anatase TiO ₂ increases.

All high refractive index polymers were also tested for trench gap fill with trenches of 1 μm (width) x 4 μm (height). All polymers show excellent gap-filling performance and does not exhibit cracking in an N ₂ environment at 400 deg.] C after 15 minutes.

All high refractive index polymers 1-5 compatible with CMP (Chemical Mechanical Milling) were also found. It has been found that prior to performing the CMP with a conventional oxide CMP slurry, the film layer is first cured at 150 ° C to 300 ° C and then an additional higher temperature cure is applied at 180 ° C to 450 ° C. When first cured at a lower temperature, the film layer is only partially cured (i.e., some of the remaining stanol remains in the film). Due to the stanol, the polymer film is still slightly hydrophilic, which is preferred when performing an oxide CMP process. All polymers are also compatible with the etch back process by using oxygen plasma. When oxygen plasma is applied, the polymer film is very uniformly etched at about 100 mm per minute, and the plasma treatment does not cause any change in reaction index, surface roughness, or defect formation. It is worth noting that conventional high refractive index organic polymers cannot perform CMP and etch back without damaging the surface quality of the film layer or changing the optical properties of the film layer.

There are also three important technical issues with the new generation of CMOS image sensors (Figure 1) that can be achieved by the chemical treatment mentioned above: device size, speed, power consumption, and quantum efficiency.

Figure 1 illustrates: 10 semiconductor substrate; 20 photodiode; 30 metal line, inter-layer dielectric (ILD) and inter-metal dielectric (IMD); 40 color filter Chip array layer; 50 microlens array; 100 high refractive index siloxane polymer filled with high aspect ratio photodiode gap; 200 for color filter planarization and protection of high refractive index 矽 oxygen An alkane polymer; and 300 a helium oxide polymer that protects the microlens.

Device size: The smaller the pixel, the greater the number of pixels on the same area (ie, the improved field factor). This can be achieved by reducing the lens size, the size of the diode, thinning the metallization and coating multiple metal layers.

Speed: shortening the metal line, improving the conductor Cu to Al and lowering the k value of the dielectric will improve speed and reduce power consumption.

Quantum efficiency: This is an opportunity to improve efficiency by using new materials that bring light into the lens and transmit it to the diode.

The material is deposited prior to the color filter array and cured at a relatively high temperature to lock its mechanical properties and is compatible with other materials used in wafer construction. The material deposited after the color filter deposition must be fully cured at a lower temperature (about 250 ° C or below). The materials of the present invention are well suited for applications above and below color filter arrays.

Maximizing quantum efficiency: Light incident on the lens is focused and passed through the color filter and transmitted to the diodes in the device layer. The goal is to maximize the amount of light that reaches the diode. For example, materials directly on the diode need to be transparent and deliver the greatest amount of light. The sidewall interface of material 100 in Figure 1 is a source of light loss due to refraction and reduces the light reflected into the diode. A simple solution is to line the sidewall with a reflective coating, but the approach will add cost and will be very difficult. Again, CVD metal deposition will make the channel narrower (reducing light transmission) and eventually pinch off at the top due to narrow features. However, if the material 100 has a higher index of refraction than the material used to form the wall immediately adjacent thereto, the refraction will be minimized and more light will be directed to the diode. Thus, metallization is surrounded by CVD SiO ₂ forming the sidewalls of the light tunnel. The CVD oxide has a refractive index of approximately 1.46 in the 632.8 nm wavelength range, so the optical channel needs to have a refractive index of > 1.46 to reduce refraction at the interface. Therefore, this is basically a vertical waveguide that transmits light to the diode. Therefore, materials based on the polymer from Example 19 having a high refractive index will play a good role in this application. This is a transparent film and will therefore be mechanically compatible with adjacent CVD SiO ₂ . The polymer from Example 19 had a refractive index of 1.65 and would therefore increase the reflectance of light from the oxide sidewall having a refractive index of 1.46. Although this material can be cured at a low temperature of 250 ° C, it can also be cured at a higher temperature exceeding 400 ° C to be compatible with the processes required in the case of Al, Cu, and SiO ₂ . In addition, the aspect ratio of the channel is increased by making the device smaller and metallization shortening to improve speed.

Color Filters and Lens Protection: The material on the color filter array (200 in Figure 1) is another opportunity to reduce the cost of the device. The polymer from Example 18 made visible light transparent and effectively blocked UV, thus protecting both the color filter and the diode and signal noise. Again, the polymer from Example 18 is an excellent planarizing material and an effective protective layer. The polymer also matches the refractive index between the color filter layer and the microlens layer, thus reducing reflection from the interface of the film layer. Also, the material can be cured at a low temperature of about 200 ° C and thus does not cause thermal degradation of the organic color filter material.

10. . . Semiconductor substrate

20. . . Photodiode

30. . . Metal lines, interlayer dielectrics, and intermetal dielectrics

40. . . Color filter array layer

50. . . Microlens array

100. . . High refractive index siloxane polymer filled with high aspect ratio photodiode gap

200. . . High refractive index siloxane polymer for planarization and protection of color filters

300. . . Protecting microlens a naphthenic polymer

Figure 1 shows a schematic cross-sectional view of a CMOS image sensor device.

Figure 2 shows a thermogravimetric chart of the high refractive index polymer 3.

Figure 3 shows a thermogravimetric chart of the high refractive index polymer 4.

Figure 4 shows an FTIR spectrum of refractive polymer 5.

10. . . Semiconductor substrate

20. . . Photodiode

30. . . Metal lines, interlayer dielectrics, and intermetal dielectrics

40. . . Color filter array layer

50. . . Microlens array

100. . . High refractive index siloxane polymer filled with high aspect ratio photodiode gap

200. . . High refractive index siloxane polymer for planarization and protection of color filters

300. . . Protecting microlens a naphthenic polymer

Claims (25)

A semiconductor device comprising: a semiconductor substrate; a plurality of photodiodes disposed in the semiconductor substrate; a metal line and a dielectric material on the substrate as an interconnect layer, the interconnect a layer defining an aperture at the photodiode; a first polymer filling a gap to cover the photodiode; a color filter layer disposed in the gap relative to the photodiode Filling the polymer layer, and the color filter layer and the gap-fill polymer layer are in contact with each other; a second polymer disposed on the interconnect layer to cover and planarize and protect the color a filter layer; a plurality of microlenses disposed on the planarized second polymer with respect to the color filter; and a third polymer layer disposed on the microlens to protect the The microlens; wherein at least one of the polymer materials comprises a siloxane polymer. The semiconductor device of claim 1, wherein each of the three polymeric materials is an organosiloxane polymer. The semiconductor device of claim 1, wherein at least one of the polymers comprises a siloxane polymer having -Si-O-Si- and -Si-(CH _x ) _{a y-} Si- group, wherein x is an integer of 1 or 2 and y is an integer between 1 and 20. The semiconductor device of claim 3, wherein the three polymers all comprise a siloxane polymer having -Si-O-Si- and -Si-(CH _x ) _{a y-} Si- group, wherein x is an integer of 1 or 2 and y is an integer 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. 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. The semiconductor device according to any one of claims 1 to 4, wherein the polymer has a refractive index of greater than 1.60 at a wavelength of 632.8 nm or higher, and a dielectric constant of 4.0 or less ( 1MHz). The semiconductor device according to any one of claims 1 to 4, wherein the polymer has a refractive index of greater than 1.60 at a wavelength of 632.8 nm or higher, and a dielectric constant of 3.5 or less ( 1MHz). The semiconductor 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 Young's modulus higher than 4.0 Gpa. . The semiconductor device of claim 1, wherein the polymer is a polymer that is heat curable at a temperature between 180 ° C and 450 ° C. The semiconductor device of claim 10, wherein the polymer is a polymer that can be combined with heat and ultraviolet light to cure. The semiconductor device according to claim 10, wherein The polymer is a heat curable polymer and can be further subjected to chemical mechanical polishing after thermal curing. The semiconductor device according to claim 10, wherein the polymer is a heat curable polymer, and after heat curing, etching can be performed by a dry etching plasma process. The semiconductor device according to any one of claims 10 to 13, wherein the polymer is a UV-treated polymer. The semiconductor device according to any one of claims 10 to 13, wherein the polymer is a heat curable polymer, and after thermal curing, can be further processed by chemical mechanical polishing and then finally subjected to a final treatment. Heat or UV curing. The semiconductor device according to claim 1, wherein at least one of the polymer and the color filter layer or the microlens layer has a refractive index difference of less than 0.1 in a visible light wavelength range. The semiconductor device of claim 16, wherein at least one of the polymer and the color filter layer or the microlens layer has a refractive index difference of less than 0.05 in the visible wavelength range. The semiconductor device of claim 1, wherein the first polymer has a refractive index that is at least 1% higher than the material defining the aperture. The semiconductor device of claim 18, wherein the first polymer has a refractive index that is at least 5% higher than the material defining the aperture. The semiconductor device of claim 1, wherein at least one of the polymers comprises a chemical structural formula: Wherein R ₁ is a hydrolyzable group; R ₂ is an organic crosslinking group, a reactive cleavage group, a polarizing reducing organic group or a combination of all of the foregoing, which includes an alkyl group, an alkenyl group, an alkynyl group An aryl group, a polycyclic group, and an organic group-containing group; and R ₃ is a bridged or branched divalent hydrocarbon group, an aromatic group, a polyaryl group or a polycyclic group. The semiconductor device according to claim 1, wherein the polymer material is modified by adding nanoparticles. The semiconductor device according to claim 21, wherein the polymer is a combination of 1 to 500 parts by weight of nanoparticles and 100 parts by weight of the polymer to form a composition containing nano particles. The semiconductor device according to claim 22, wherein the polymer is combined with about 5 to 100 parts by weight of the nanoparticles and 100 parts by weight of the polymer to form a composition containing the nanoparticles. The semiconductor device according to claim 23, wherein the polymer is combined with about 10 to 50 parts by weight of the nanoparticles and 100 parts by weight of the polymer to form a composition containing the nanoparticles. The semiconductor device according to claim 21, wherein The nanoparticles are selected from the group consisting of metals, metal alloys, metal oxides, carbides, and nitrides, and mixtures thereof.