TWI512931B - Barrier film formation method and IC chip package - Google Patents

Description

Method for forming barrier film and IC chip package

The present invention relates to a method for forming a barrier film and an IC chip package, and more particularly to a method for forming a barrier film by an evaporation polymerization method and an IC chip package having the barrier film.

In the past, in the field of semiconductor devices (IC chips), there is a technique of wire bonding, which is a technique for electrically connecting a device to a device after fabricating a device on a germanium wafer. . However, as the device is miniaturized, the pitch of the connected steel wires is narrowed, and the connection work becomes a difficult problem. In addition, the signal delay due to the steel wire becomes a serious problem. At the same time, the miniaturization of the device is gradually approaching the limit, and gradually reaches the limit of large-capacity, high-speed operation.

Therefore, a technique for this solution has been gradually developed in which the devices are overlapped, and then burrowed, and the wiring film made of Cu or Al buried in the hole is connected. For example, in the field of flash memory, a large-capacity flash memory in which a plurality of pieces of memory are superimposed is partially productized. These technologies are collectively referred to as TSV or 3D installation. In the memory system as described above, a device in which a plurality of identical devices are stacked to obtain a capacity, or a memory device and a different device such as a logic circuit are overlapped to shorten wiring, and a high-speed operation is performed. The combination is freely chosen for the purpose.

In the TSV technology, the system can be roughly divided into first through hole projects and After the through hole project, the first through hole project is performed before the IC chips (or the germanium wafers) are connected to each other, and a hole is formed to embed a Cu film as a wiring film; the through hole project is followed by opening a hole. A Cu film or the like is formed.

In the above-mentioned through-hole engineering, the adhesive is also contained and a hole is opened to embed Cu. Therefore, the maximum temperature of the process depends on the heat resistance of the adhesive. Although it varies depending on the type of the adhesive, it is generally preferably 200 ° C or less.

On the other hand, the shape of the hole is 2~20μm, and the depth is about 50~200μm. Therefore, the aspect ratio (A/R) is about 10 to 100. Uniform film formation in such a hole of A/R is not possible by the conventional sputtering method, and therefore it is required to be carried out by the CVD method.

In addition, the barrier films used in the semiconductor device fabrication process are mainly Ti, TiN, Ta, and TaN films formed by the CVD method (for example, refer to Patent Document 1), and the film formation temperature is as high as possible. At 300 ° C or higher, it cannot be used in a project using a TSV technology which is intended to be carried out at a low temperature. That is, it is seeking to develop a new barrier film for engineering using TSV technology. Further, conventionally, the wiring film is formed on the SiO ₂ film, and therefore, the barrier film can be a conductor. However, in the engineering using the TSV technology, since the base is made of a conductor (semiconductor), the barrier film is also required to have insulation properties. Therefore, for material properties, it must also be developed.

Generally, a Cu film is formed as a wiring film by a CVD method on the above barrier film according to a well-known method (for example, refer to the patent document) Offer 2).

Further, as described above, in the prior art, a film of a metal or a metal nitride is generally formed by a sputtering method or a CVD method, and is used as a barrier film of a wiring film of Cu or Al. In particular, if the A/R is increased (for example, 5 or more), the CVD method must be used. Therefore, since an organic metal material or a metal chloride or fluoride is used as a barrier film material, the film formation temperature is generally 300 ° C or higher. In the case of an organometallic material, in order to decompose and remove the organic matter, heat energy due to high temperature is required. Further, in the case of a metal chloride or a fluoride, although the reaction temperature is generally low, in order to remove chlorine or fluorine from the film, high temperature is required. Further, in the prior art, in order to prevent oxidation of the surface of the barrier film made of metal or the like, it is necessary to continuously form Al or Cu or the like in a vacuum after the formation of the barrier film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2010/007991

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-081431

An object of the present invention is to solve the above problems of the prior art, and to provide a barrier which is excellent in insulating properties, barrier properties, and uniform film forming properties in a hole by a so-called vapor deposition polymerization method. Film method, and IC chip package having the barrier film; the vapor deposition polymerization In the method, two kinds of monomers are simultaneously vapor-deposited in a vacuum to be reacted on a substrate, and then heated as needed, and a desired film is obtained by a polymerization reaction.

The invention of the first method for forming a barrier film of the present invention is to deposit and bond a plurality of germanium wafers on which an IC wafer is formed, and to bond the germanium wafer by TSV technology. A method for electrically connecting the IC chips to each other, and then forming a barrier film in the hole before the plurality of IC chips are connected in series and forming a conductor film in the hole is characterized by: Two or more kinds of monomers are evaporated in a vacuum, and a barrier film composed of polyimine is formed in the hole by an evaporation polymerization method.

In the invention of the first aspect of the invention, the monomers are vaporized simultaneously or separately.

In the invention of the first formation method, the monomer is composed of an aromatic diamine and a tetracarboxylic dianhydride.

The invention of the second method for forming a barrier film of the present invention is to deposit and bond a plurality of wafers on which an IC wafer is formed, and to bond the germanium wafer by TSV technology. A method for electrically connecting the IC chips to each other, and then forming a barrier film in the hole before the plurality of IC chips are connected in series and forming a conductor film in the hole is characterized by: Two or more kinds of monomers are evaporated in a vacuum, and a barrier formed of a polymer is formed in the hole by an evaporation polymerization method. membrane.

In the invention of the second formation method described above, the monomers are vaporized simultaneously or separately.

In the invention of the second formation method described above, the polymer is a polyimine.

In the invention of the second formation method, the monomer is composed of an aromatic diamine and a tetracarboxylic dianhydride.

The invention of the first IC chip package of the IC chip package of the present invention is an IC chip package having a germanium wafer laminate in which a plurality of wafers of a plurality of wafers each having an IC wafer are formed and stacked. It is characterized in that a hole opened by the TSV technology is provided on the tantalum wafer laminate, and two or more kinds of monomers are formed and vapor-deposited in the hole. A barrier film composed of polyimine is formed, and then a conductor film is formed on the barrier film.

In the invention of the first IC chip package, the monomer is composed of an aromatic diamine and a tetracarboxylic dianhydride.

The invention of the second IC chip package of the IC chip package of the present invention is an IC chip package having a germanium wafer laminate in which a plurality of wafers of a plurality of wafers each having an IC wafer are formed and stacked. The feature is that a hole formed by the TSV technology is disposed on the germanium wafer laminate, and a hole formed by vapor deposition polymerization is formed in the hole. A barrier film is then formed on the barrier film with a conductive film.

In the invention of the second IC chip package, the polymer is a polyfluorene Imine.

In the invention of the second IC chip package, the monomer is a vapor deposition polymer of an aromatic diamine and a tetracarboxylic dianhydride.

According to the present invention, it is possible to form a film at 250 ° C or lower by a vapor deposition polymerization method in a hole opened by a TSV technique, and to sufficiently exhibit plating ability even when A/R is 10 or more (throwing) Power), forming a barrier film that can be fully used as a barrier film.

Further, according to the present invention, the IC chip package including the barrier film described above has the problem that the signal delay does not occur, and large-capacity and high-speed operation is also possible.

Hereinafter, an embodiment of a method for forming a barrier film of the present invention and an embodiment of an IC chip package will be described, and each constituent element will be described in detail later.

According to an embodiment of the method for forming a barrier film of the present invention, the formation method is to form a plurality of wafers of an IC wafer (IC device) on a surface of a germanium wafer so that an IC wafer is not formed. The back side of the wafer is deposited in contact with the surface side of the other germanium wafer on which the IC wafer is formed, and bonded using an adhesive selected from, for example, a decane resin or an epoxy resin, and is bonded by 3D. Installation engineering (TSV technology, engineering), and on the bonded germanium wafer laminate, to open the IC wafers to each other a hole to be connected, and then a barrier film is formed in or around the hole before forming a conductor film made of Cu, Al, W, or Ni in a plurality of IC chips in series in a hole or a periphery thereof The method comprises two or more monomers, preferably an aromatic diamine and a tetracarboxylic dianhydride, which are evaporated in a vacuum, and e.g., each monomer is simultaneously evaporated or the time is shifted and evaporated separately. Further, it is formed by vapor deposition polymerization in or around the hole to form a barrier film composed of a polymer such as polyimide or the like. In the present specification, the case of "inside the hole" is set to include the inside of the hole and its surroundings. At this time, the film formed around the hole is etched and removed in response to the target device.

In addition, according to the embodiment of the IC chip package of the present invention, the IC chip package has respective wafers of a plurality of wafers on which IC chips are respectively formed, so that the silicon wafers on which the IC wafers are not formed are formed. The back side is deposited in such a manner as to be in contact with the surface side of the other tantalum wafer on which the IC wafer is formed, and the tantalum wafer laminate is bonded by an adhesive selected from, for example, a siloxane resin or an epoxy resin. On the enamel wafer laminate, a hole opened by TSV technology is provided after bonding, and two or more kinds of monomers are formed in or around the hole, and it is preferable to use an aromatic two. a barrier film made of a polymer such as polytheneimide obtained by vapor-depositing an amine and a tetracarboxylic dianhydride, and then formed on the barrier film by Cu, Al, W or Ni. It is made up of a conductive film.

In the prior art, as described above, a metal or a metal nitride is formed by a sputtering method or a CVD method as a barrier film for a wiring film. In particular, if the A/R is increased (for example, 5 or more), the CVD method must be used. because Further, the film forming temperature is required to be caused by heat of 300 ° C or higher, and in addition, high temperature is required in order to remove chlorine or fluorine from the raw material used from the film. Further, in the prior art, in order to prevent oxidation of the surface of the metal-containing barrier film, it is necessary to continuously form a wiring film in a vacuum after the barrier film is formed.

However, according to the present invention as described above, since the barrier film is a polymer film composed of an organic material, the film formation temperature is also low, and the obtained silicon wafer can be temporarily taken out after the formation of the polymer film. In the atmosphere, the next project will be carried out.

Further, in the case of the present invention, when annealing treatment is necessary, it is also possible to form a film of Al, Cu or the like after annealing.

Further, in order to improve the adhesion of the Al or Cu film to the barrier film, it may be added before or during film formation of the polyimide or before or after the film formation of Al or Cu (after annealing). The amount of the following decane coupling agent to be added is, for example, about 0.01 to 0.1 mol based on 1 mol of the polyimine, and is added in a small amount to the polyimine. Add a degree such as 10 molecular layers.

The polymer constituting the barrier film which can be formed according to the present invention may, for example, be a polyimine, a polyamine, a polymethylenimine, a polyurea or a mixture of any of these, and the like. A polyimine can be cited.

As the aromatic diamine which is a monomer which can form one of the above polyimines, for example, 4,4'-diphenyl ether, 1,4-diamine benzene, 1, can be used. 3-diamine benzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4 , 4'-diamine linkage Benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,7- Diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminodiphenyl benzophenone, 3',3'-diaminodiphenyl ketone, 4,4'-bis(4-aminophenyl) sulfide, 4,4'-diaminodiphenyl hydrazine, 4,4'-diaminobenzimidamide, 1,n-bis(4- Aminophenoxy)alkane, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,2-bis[2-(4-aminophenoxy)B Oxy]ethane, 9,9-bis(4-aminophenyl)anthracene, 5(6)-amino-1-(4-aminomethyl)-3,3,3-trimethylhydrazine Full, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis(4-aminophenoxybenzene) Propane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4 -aminophenoxy)phenyl]hexafluoropropane, 3,3'-dicarboxylic acid-4,4'-diaminodiphenylmethane, 4,6-dihydroxy-1,3-diphenylamine, 3 , 3'-hydroxy-4,4'-diamino Benzene, 3,3',4,4'-tetraaminobiphenyl, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, and 1,3-double ( At least one selected from the group consisting of 3-aminopropyl)-1,1,3,3-tetramethyldioxane.

Further, as the tetracarboxylic dianhydride which is another monomer which can form a polyimine, for example, pyromellitic dianhydride, oxydiphthalic dianhydride, biphenyl can be used. -3,4,3',4'-tetracarboxylic dianhydride, diphenyl ketone-3,4,3',4'-tetracarboxylic dianhydride, diphenyl hydrazine-3,4,3',4 '-tetracarboxylic dianhydride, 4,4'-(2,2-hexafluoroisopropene) diphthalic dianhydride, m(p)-triphenyl-3,4,3',4'-four Carboxylic dianhydride, cyclobutane 1,2,3,4-tetracarboxylic dianhydride, and 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6:3,5- The dianhydride and the like are selected at least 1 species.

In the case of the vapor deposition polymerization of the present invention described above, a solution polymerization method (for example, using dimethylformamide or the like as a solvent) is carried out to obtain a polyamic acid solution, followed by a solution of a polyamic acid solution. The method of removing the solvent and performing dehydration ring closure to obtain a polyimide film is the same as long as it is appropriately selected from the aromatic diamine and the tetracarboxylic dianhydride which can be generally used in the solution polymerization method exemplified above. Similarly, a polyimine film obtained by vapor deposition polymerization can be obtained.

As the above-described decane coupling agent, an organic ruthenium compound having a functional group reactively bonded to an organic material and a functional group bonded to an inorganic material in a molecule, and having a structure of a secondary formula is known. Wait.

ZR-Si-(X) ₂

In the above formula, Z is a functional group reactively bonded to an organic material, and is, for example, a vinyl group, an epoxy group, an amine group, a methacryl group, or a thiol group, and the X system and the inorganic group. The functional group or halogen atom in which the material is reacted, and is, for example, an alkoxy group selected from a methoxy group, an ethoxy group or the like, an ethoxy group, a phenoxy group, or a chlorine atom.

As described above, in order to improve the adhesion of the wiring film composed of the Al film or the Cu film to the barrier film, a specific amount of the decane coupling agent may be added in a specific order according to a known method. Listed below.

For example: except 3-aminopropyltrimethoxydecane, 3-aminopropyltriethyl Oxy decane, 3-(2-aminoethyl)aminopropyltrimethoxy decane, 3-(2-aminoethyl)aminopropyltrimethoxy decane, 3-phenylaminopropyltrimethoxy decane 1,2-ethanediamine, N-{3-(trimethoxydecyl)propyl}-, N-{(vinylphenyl)methyl} derivative. Hydrochloride 40% Methanol solution, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-ring Oxycyclohexyl)ethyltrimethoxy decane, vinyltriethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, propylene trimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-methacryloyloxypropylmethyldimethoxydecane, 3-thiolpropyltrimethoxyoxane, 3-thiolpropylmethyldimethoxydecane, 3-thiolpropyltriethoxydecane, In addition to amino decane (methanol solution), amino decane mixture, and amino decane (IPA solution), methyl trimethoxy decane, dimethyl dimethoxy decane, and trimethyl methoxide can be used. Methoxy methoxy methoxy, methyl triethoxy Alkenyloxy, methyltriphenyloxane, ethyltrimethoxydecane, n-propyltrimethoxydecane, diisopropyldimethoxydecane, isobutyltrimethoxydecane, diisobutyldimethoxydecane , isobutyl triethoxy decane, n-hexyl trimethoxy decane, n-hexyl triethoxy decane, cyclohexyl methyl dimethoxy decane, n-octyl triethoxy decane, n-decyl trimethoxy decane, And phenyltrimethoxy decane, as methyl chlorodecane, dimethyl dichloro decane, trimethyl chloro decane, and n-octyl dimethyl chloro decane, tetraethoxy decane and 1, 1 , 1,3,3,3-hexamethyldioxane, and methyl methoxy siloxane as an oligomer, methyl methoxy decane, dimethyl-phenyl methoxy At least one selected from the group consisting of decane, diethyl-phenylmethoxy methoxy oxane, and alkyl alkoxy oxane.

The above decane coupling agent is prepared by a well-known method (for example, JP-A-2006-231134) before or during film formation of a polyimide or before film formation of Al or Cu or the like ( After annealing, the desired amount may be added.

Next, a film forming apparatus for carrying out the method for forming a barrier film of the present invention will be described with reference to a first drawing which shows a schematic structural example.

The film forming apparatus 1 shown in Fig. 1 has a vacuum chamber 11 on which a substrate S to be processed is placed, and the vacuum chamber 11 is provided with an exhaust system 12 for decompressing the inside of the vacuum chamber. In the vacuum chamber 11, a tungsten boat 13a for the first raw material monomer (A) and a tungsten boat 13b for the second raw material monomer (B) are disposed, and the tungsten boat 13a and the tungsten boat 13b are disposed. Upper portions are provided with shutters 14a and 14b, respectively. The substrate S to be processed is placed and fixed on the carrier 15, and the surface is treated to be disposed in the vacuum chamber 11 so as to face the first and second raw material monomers (A and B). Above. Further, although not shown, the tungsten boat 13a and 13b are provided with heating means for generating a vapor of a raw material of a solid or a liquid.

Further, when the first and second raw material monomers (A and B) are solid at room temperature, although not shown, the tungsten boat 13a and 13b are respectively provided with a monomer for mounting. It is preferable that the evaporation amount is adjusted to the same slit plate.

In the case where the barrier film is formed by using the above-described film forming apparatus 1, for example, first, a first semiconductor element region (IC wafer) is formed on the surface by using an adhesive such as a decane resin or an epoxy resin. First wafer The front side is joined to the back side of the second silicon wafer on which the second semiconductor element region (IC wafer) is formed. The second semiconductor element region to be formed on the second germanium wafer is formed on the second germanium wafer by the TSV technology and dry etching to form the second semiconductor device layer formed on the second germanium wafer under specific process conditions. A hole in the first semiconductor element region on the wafer is electrically connected. A tantalum wafer laminate having a hole is used as the substrate S to be processed of the present invention.

For the etching by the TSV technology, reference is made to FIG. 2 showing a schematic structure example of an IC chip package including a germanium wafer laminate having a first germanium wafer and a second germanium wafer. Description.

The IC chip package 2 shown in FIG. 2 passes through the surface layer side of the first silicon wafer 21 and the back surface side of the second silicon wafer 22 through an adhesive layer made of a siloxane resin or an epoxy resin. 23, and as a strategist. A part of the surface layer of the first wafer 21 is formed by a well-known method in which a first semiconductor element region (IC wafer) 21a is formed, and a part of the surface layer of the second wafer 22 is known. The second semiconductor element region (IC wafer) 22a is formed by the method. Further, an insulating layer 24 is provided between the first silicon wafer 21 and the adhesive layer 23, and an insulating layer 25 is provided between the second germanium wafer 22 and the adhesive layer 23. The second IC wafer 22a to be formed on the second germanium wafer 22 and the first germanium wafer 21 are formed for the germanium wafer laminate by the TSV technology and under specific dry etching conditions. The first IC chip 21a is a hole for electrical connection. In the hole thus obtained and its periphery, as described above, two or more kinds of monomers are used, and more preferably an aromatic diamine and a tetracarboxylic dianhydride are used. The barrier film 26 composed of a polymer such as polyimide or the like is formed by vapor deposition polymerization. Then, the bottom of the hole (hole) of the barrier film 26 is removed by etching, and then formed on the barrier film 26 and the exposed first semiconductor element region 21a by Cu, Al, W, or Ni. The conductor film 27 is formed. Thus, the IC chip package 2 of the present invention is obtained.

The dry etching is performed, for example, via a SiN hard mask (for example, a thickness of 0.5 μm) provided on the second silicon wafer 22. In other words, the second IC wafer 22a, the second silicon wafer 22, the insulating layer 25, the adhesive layer 23, and the insulating layer 24 are sequentially etched and etched onto the first IC wafer 21a. Connect the hole.

The etching process of the above mask is, for example, setting the pressure in the vacuum chamber to 0.67 Pa, and allowing Ar/C ₄ F ₈ /O ₂ gas to flow at a flow rate of 180/20/10 sccm, and using it as a high antenna. 1200 W was applied to the power supply of the frequency power supply, and 400 W was applied to the power supply from the high-frequency power supply for bias voltage.

The etching process of the second wafer 22 (for example, a thickness of 10 μm) is, for example, setting the pressure in the vacuum chamber to 6.65 Pa, and allowing the SF ₆ /O ₂ /HBr gas to flow at a flow rate of 150/55/0 sccm. In addition, 1000 W was applied as power supply from the high-frequency power source for the antenna, and 50 W was applied as the power supplied from the high-frequency power source for bias voltage.

An etching process of an insulating layer (for example, a thickness of 0.5 μm) composed of SiO ₂ is, for example, setting the pressure in the vacuum chamber to 2 Pa, and letting Ar/C ₄ F ₈ / at a flow rate of 180/20/10 sccm / The O ₂ gas flows and is applied as 1200 W from the supply power of the high-frequency power source for the antenna, and is applied by applying 400 W to the power supplied from the bias high-frequency power source.

The etching process of the above-mentioned adhesive layer 23 is, for example, setting the pressure in the vacuum chamber to 1.5 Pa, and allowing the SF ₆ /O ₂ /N ₂ gas to flow at a flow rate of 30/200/85 sccm, and serving as an antenna. 2000 W was applied to the power supply of the high-frequency power source, and 300 W was applied to the power supplied from the high-frequency power source for bias voltage.

By the insulating layer formed of SiO _2, for example, as long as the TEOS-based gas as a raw material, and process conditions it is well known (e.g., see Japanese Laid-Open Patent Publication No. 2001-345315) can be formed next.

The substrate S thus obtained is placed on the holder 15 and fixed. Further, the first raw material monomer A (for example, tetracarboxylic dianhydride such as pyromellitic dianhydride) and the second raw material monomer B (for example, aromatics such as 4,4'-diphenyl ether) The diamine) is filled in the tungsten boat 13a and 13b for evaporation in the vacuum chamber 11 of the film forming apparatus 1 shown in Fig. 1, and the bracket 15 on which the substrate S to be processed is placed and fixed is provided. Above the inside of the vacuum chamber 11.

Next, after evacuating the inside of the vacuum chamber 11 to a specific pressure (for example, 1E-4Pa), each of the tungsten boats 13a and 13b is heated to a specific temperature at which each of the monomers A and B can generate steam. And opening the gates 14a and 14b so that the vapors of the first raw material monomer and the second raw material monomer are simultaneously scattered at the same time, or the gates 14a and 14h are alternately opened to respectively make the respective vapors. Each of them is scattered in a random manner, and is vapor-deposited on the substrate S to be processed to form a polyimide acid film having a specific film thickness. In the case where both raw materials are solid at room temperature, although not shown, the slit plates for the same evaporation amount are attached to the tungsten boat 13a and 13b to form each of the moire. The evaporation of the ground is ideal. On the substrate S to be processed, the raw material monomers A and B are reacted at the moment of molecular doping to form a polyamide acid. Then, annealing is performed at a specific temperature (for example, 250 ° C or lower), between specific times, in an inert environment such as an N ₂ atmosphere. In this way, the polyamic acid ruthenium can be imidized, and the target barrier film composed of the polyimide film can be obtained.

When the substrate S to be processed is carried into another CVD apparatus, a Cu film or an Al film having a specific thickness as a wiring film is formed under a known process condition (for example, JP-A-2009-130288). The IC chip package of the present invention can be obtained. A barrier film having excellent insulating properties, barrier properties, and uniform film forming properties in the pores at a film forming temperature of 250 ° C or lower is formed.

[Example 1]

An example of a case where a polyimide film is formed as a barrier film is shown. In the present embodiment, using the film forming apparatus shown in Fig. 1, the pyromellitic dianhydride as the first raw material monomer (A) and the 4, 4' as the second raw material monomer (B), respectively. - Diphenyl ether, which is filled in the tungsten boat 13a and 13b for evaporation, and the silicon wafer S fixed on the carrier 15 is carried into the vacuum chamber 11, and is exhausted to 1E-4Pa, and further, tungsten is used. The boats 13a and 13b are heated to a specific temperature, and the gates 14a and 14b are opened, so that the vapors of the pyromellitic dianhydride and the 4,4'-diphenyl ether are simultaneously scattered and formed at the same time. A polyamic acid film having a thickness of 300 nm. Since both raw materials are solid at room temperature, although not shown, the slit plates for the same evaporation amount are attached to the tungsten boat 13a and 13b. On the tantalum wafer S, pyromellitic dianhydride and 4,4'-diphenyl ether are reacted at the instant of molecular doping to form polyamic acid. Thereafter, an annealing treatment was performed in an N ₂ atmosphere between 6 hours at 150 °C.

From this, it can be seen that 80% or more of them are those which undergo imidization. The tantalum wafer S was transferred into another Cu-CVD apparatus, and a Cu film having a thickness of 30 nm was formed under well-known process conditions. The tantalum wafer S on which the Cu film was formed was taken out, and the cross section thereof was observed by SEM, and the film thickness of the polyimine on the tantalum wafer S at each portion was measured. The Cu film is formed to confirm adhesion. The film thickness of the polyimide film to be measured at each site is shown in Table 1 below.

The tantalum wafer S used in the present embodiment has a hole pattern having a hole diameter of 5 μm, a depth of 50 μm, and a thickness of 70 μm. The film thickness measurement portion on the wafer S is as shown in FIG. 3, which is the surface A above the wafer S, the upper portion B of the sidewall in the hole, the middle portion C of the sidewall in the hole, and the lower portion D of the sidewall in the hole. Lower part E inside the hole.

According to Table 1, it can be seen that a very uniform polyimide film can be formed at any of the depths of 50 μm and 70 μm at a hole diameter of 5 μm. Further, in the above observation, it is understood that since the Cu film is not peeled off, sufficient adhesion can be obtained.

Next, while changing the film thickness of the polyimide film, a 0.5 mm portion is formed on the surface of the germanium wafer having no hole pattern. The Al film was applied with a voltage between the Al film and the germanium wafer to measure the VI characteristics. The relationship between the film thickness (nm) of the polyimide film and the current density (leakage current density (A/cm ² )) when the actual voltage is applied to 3 V is shown in Fig. 4.

As can be seen from Fig. 4, the leakage current decreases as the thickness of the polyimide film increases, but becomes higher as the film thickness becomes thinner. Although the leakage current is high, although it is a less desirable property in practical use, it can be said that it is only 10 ^-7 A/cm ² at a film thickness of 200 nm and a value of 10 ^-8 A/cm ² at 300 nm. For the purpose of adjusting the film thickness, it is possible to obtain a practical value.

[Embodiment 2]

An infrared absorption (IR) spectrum was measured for the film formed by vapor deposition polymerization according to the method described in Example 1.

Next, the change in the IR spectrum at 100 ° C and 150 ° C was measured to determine the formation ratio of polyamic acid and polyimine in the deposited film. The results are shown in Figure 5.

In Fig. 5, the horizontal axis represents the elapsed time (hr), and the vertical axis represents the amidation ratio (%) and the oxime imidization ratio (%). Respectively, the maximum value of absorption 1650cm ^{-1 -1,} 1380 cm 100%, based on the measurement of the absorption depth of each of the determined time. As can be seen from Fig. 5, the film immediately after vapor deposition at 100 ° C is about 100% polyacrylic acid, and is subjected to amide amination by heating. It can be seen that if the temperature is raised to 150 ° C, over time, the polyamide acid will dehydrate and change to polyimine. After 6 hours, about 80% will change into polyimine.

[Example 3]

The vapor deposition polymerization was carried out in accordance with the method described in Example 1, to form a polyimide film. However, the switches of the gates 14a and 14b are adjusted so that the vapors of the pyromellitic dianhydride and the 4,4'-diphenyl ether are scattered at each time, and are formed on the silicon wafer S. Polyimine film of a specific thickness.

As a result, a uniform Cu film was formed in a portion having a depth of 5 μm and a depth of 50 μm and 70 μm, which was slightly equal to the results shown in Table 1, and the Cu film was not peeled off. Further, when the V-I characteristic was measured as in the case of Example 1, the leakage current and the film of the polyimide film were measured. The thick relationship is the same as in the case of Fig. 4, and as long as the film thickness is adjusted in accordance with the purpose, a practical value can be obtained.

[Industrial availability]

According to the present invention, there is provided a method for forming a hole for electrically connecting IC chips to each other on a bonded germanium wafer by a TSV technology, and then forming a barrier film in the hole, which is The above-mentioned monomers are evaporated in a vacuum, and a barrier film can be formed on the surface of the hole at a film forming temperature of 250 ° C or lower by a vapor deposition polymerization method, and the A/R is sufficient even if it is 10 or more. The barrier film which exhibits the plating ability and can be fully used, and the IC chip package having the barrier film can be utilized in the field of semiconductor devices using TSV engineering.

1‧‧‧ film forming device

S‧‧‧Processed substrate (wafer)

11‧‧‧vacuum tank

12‧‧‧Exhaust system

13a, 13b‧‧‧ (evaporation) tungsten boat

14a, 14b‧‧ ‧ gate

15‧‧‧ bracket

A‧‧‧First raw material monomer

B‧‧‧Second raw material monomer

2‧‧‧IC chip package

21‧‧‧1st wafer

21a‧‧‧1st semiconductor device area (IC chip)

22‧‧‧2nd wafer

22a‧‧‧2nd semiconductor device area (IC chip)

23‧‧‧ adhesive layer

24, 25‧‧‧Insulation

26‧‧‧Block film

27‧‧‧Electrical film

[Fig. 1] A schematic view showing a structural example of a film forming apparatus for carrying out the method for forming a barrier film of the present invention.

[Fig. 2] is a cross-sectional view showing a schematic structural example of an IC chip package.

[Fig. 3] is a schematic cross-sectional view of a tantalum wafer for explaining a portion where the film thickness of the polyimide obtained in Example 1 is measured.

[Fig. 4] is a graph showing the relationship between the film thickness (nm) of the polyimide film obtained in Example 1 and the current density (leakage current density (A/cm ² )) at the time of voltage application.

[Fig. 5] is shown in Example 2, according to the film for vapor deposition A graph showing the relationship between the production rate of polyamic acid and polyimine of the vapor deposited film, as measured by the change in the infrared absorption (IR) spectrum, and the horizontal axis indicates the elapsed time ( Hr), the vertical axis represents the amide amination rate (%) and the oxime imidization rate (%).

Claims (11)

A method for forming a barrier film by stacking and bonding a plurality of germanium wafers on which IC chips are formed, and by using TSV technology, opening the bonded silicon wafers to electrically separate IC chips from each other A method of forming a barrier film in a hole before forming a conductor film in a hole in which a plurality of IC wafers are connected, characterized in that two or more monomers are evaporated in a vacuum Further, a barrier film made of polyimine is formed in the hole by a vapor deposition polymerization method, and a decane coupling agent is added after the formation of the polyimide or the film. The method for forming a barrier film according to the first aspect of the invention, wherein the decane coupling agent is added in an amount of 0.01 to 0.1 mol per mol of the polyimine. The method for forming a barrier film according to the first aspect of the invention, wherein after the formation of the polyimide film, the decane coupling agent is added to 10 molecules before the formation of the conductor film. A method for forming a barrier film by stacking and bonding a plurality of germanium wafers on which IC chips are formed, and by using TSV technology, opening the bonded silicon wafers to electrically separate IC chips from each other A method of forming a barrier film in a hole before forming a conductor film in a hole in which a plurality of IC wafers are connected, characterized in that two or more monomers are evaporated in a vacuum Further, a barrier film made of a polymer is formed in the hole by a vapor deposition polymerization method, and a decane coupling agent is added to the film formation of the barrier film or even after film formation. The method for forming a barrier film according to the fourth aspect of the invention, wherein, in the film formation of the barrier film, the decane coupling agent is added in an amount of 0.01 to 0.1 mol per mol of the polyimide. The method for forming a barrier film according to the fourth aspect of the invention, wherein after the barrier film is formed, the decane coupling agent is added to 10 molecules before the formation of the conductor film. The method for forming a barrier film according to any one of claims 4 to 6, wherein the monomer is composed of an aromatic diamine and a tetracarboxylic dianhydride. An IC chip package having an IC chip package for stacking and bonding germanium wafer laminates of a plurality of wafers on which a plurality of IC wafers are formed, respectively, characterized by: In the layered product, a hole opened by a TSV technique is provided after the bonding, and in the hole, a monomer obtained by using two or more kinds of monomers and vapor-deposited is formed by adding a decane coupling agent. A barrier film composed of polyimide, followed by a conductor film formed on the barrier film. The IC chip package according to claim 8, wherein the decane coupling agent in the polyimine is 0.01 to 0.1 mol based on 1 mol of the polyimine. An IC chip package having an IC chip package for stacking and bonding germanium wafer laminates of a plurality of wafers on which a plurality of IC wafers are formed, respectively, characterized by: On the stratification, it is set by the TSV technology after bonding In the hole formed, a barrier film containing a decane coupling agent composed of a polymer obtained by vapor deposition polymerization is formed, and then a conductor film is formed on the barrier film. The IC chip package according to claim 10, wherein the decane coupling agent in the barrier film is 0.01 to 0.1 mol based on 1 mol of the polymer.