WO2012070480A1 - 金属配線形成用の転写基板及び前記転写用基板による金属配線の形成方法 - Google Patents

金属配線形成用の転写基板及び前記転写用基板による金属配線の形成方法 Download PDF

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WO2012070480A1
WO2012070480A1 PCT/JP2011/076628 JP2011076628W WO2012070480A1 WO 2012070480 A1 WO2012070480 A1 WO 2012070480A1 JP 2011076628 W JP2011076628 W JP 2011076628W WO 2012070480 A1 WO2012070480 A1 WO 2012070480A1
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Prior art keywords
metal
metal wiring
transfer
wiring material
transfer substrate
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PCT/JP2011/076628
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English (en)
French (fr)
Inventor
俊典 小柏
昌昭 栗田
尚 西森
幸男 兼平
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田中貴金属工業株式会社
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Application filed by 田中貴金属工業株式会社 filed Critical 田中貴金属工業株式会社
Priority to EP11843493.5A priority Critical patent/EP2645409B1/en
Priority to US13/879,803 priority patent/US8912088B2/en
Priority to CN201180056766.6A priority patent/CN103262227B/zh
Priority to KR1020137013880A priority patent/KR101380002B1/ko
Publication of WO2012070480A1 publication Critical patent/WO2012070480A1/ja

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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
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Definitions

  • the present invention relates to a transfer substrate for forming a metal wiring on an object to be transferred such as a semiconductor wafer, a compound wafer, and a MEMS wafer, and a metal wiring method using the same.
  • the mounting method As the mounting density of electronic components such as semiconductor chips has increased, the mounting method has changed from the conventional wire bonding method to the wireless mounting method in which a semiconductor chip is directly attached to a circuit board, such as a flip chip bonding method. It is coming.
  • bumps are formed on terminal electrodes on the semiconductor chip of the device wafer or external electrodes for connection to the semiconductor chip to form metal wiring, and this is face-down bonded onto the substrate. To do. Further, before the formation of the bumps, it is common to perform a metallization process on the terminal electrodes or the like to form a barrier metal layer, and then bumps are formed thereon.
  • a plating method is generally used as a conventional method for the bump forming process.
  • the bump formed by the plating method is considered to be useful as an electrode because it is dense and has good electric conduction characteristics.
  • the bump formation by the plating method cannot sufficiently cope with the miniaturization of the metal wiring which is considered to proceed in the future. Therefore, a bump forming method by a transfer method using a transfer substrate as in Patent Document 1 has been proposed.
  • a transfer substrate in which a wiring material to be a bump is previously formed on a substrate such as glass is manufactured.
  • a transfer substrate is placed on a metallized wafer in advance and pressed and heated to transfer a wiring material onto the wafer to form bumps.
  • This method can transfer an arbitrary wiring material on the transfer substrate to an arbitrary position on the wafer by controlling the pressurization and heating, and enables miniaturization of the metal wiring and a defective sector on the wafer. Therefore, it is possible to avoid the formation of the wiring and the waste of the material.
  • the heating temperature on the wafer side is 300 to 400 ° C.
  • the heating temperature on the transfer substrate side is 100 to 200 ° C.
  • This set temperature and temperature difference cause deformation (warping) of the transfer substrate. That is, glass is often used for the transfer substrate, and there is a risk of deformation when the heating temperature exceeds 200 ° C.
  • the heating temperature of the transfer substrate itself is set to be somewhat low, if the heating temperature on the wafer side is high, the temperature of the glass substrate may be increased due to heat transfer via the bumps.
  • the heating temperature at the time of bump transfer is low, but the heating temperature on the wafer side cannot be easily lowered. This is because bumps on a transfer substrate are generally formed by a plating method, but in order to transfer bumps formed by plating to a wafer, it is necessary to cause sufficient bonding between the wafer and the bumps. This is because high temperature heating is necessary for this purpose.
  • the present invention provides a transfer substrate for forming a metal wiring on a transfer object such as a wafer by a transfer method, which can lower the heating temperature on the transfer object side than before. Also disclosed is a method of forming a metal wiring using this transfer substrate.
  • the present inventors have found the technical knowledge of the present inventors to find a transfer substrate provided with a metal wiring material having a configuration that can be transferred to a transfer object even at a low temperature. Considered in consideration. Further, it has been found that a molded body obtained by sintering a metal powder having a high purity and a fine particle diameter can be bonded to a transfer object even at a relatively low temperature, and that it functions as a metal wiring. I came up with the invention.
  • the present invention comprises a substrate, at least one metal wiring material formed on the substrate, and a base metal film formed between the substrate and the metal wiring material.
  • a transfer substrate for transferring to a transfer object wherein the metal wiring material is gold powder, silver powder, platinum powder, palladium powder having a purity of 99.9% by weight or more and an average particle diameter of 0.01 ⁇ m to 1.0 ⁇ m.
  • a molded body formed by sintering at least one metal powder selected from copper powder, and the base metal film is made of gold, silver, platinum, palladium, ruthenium, rhodium, iridium, chromium, titanium, tungsten, tantalum , Nickel, copper, zirconium, or an alloy thereof.
  • the transfer substrate according to the present invention uses a sintered body formed by sintering a predetermined metal powder as a metal wiring material (bump) to be transferred to an object to be transferred (wafer).
  • the metal wiring material made of this sintered body is porous, unlike the dense material formed by plating of the prior art, and is in contact with the surface of the transfer object in point contact during transfer.
  • the temperature required for joining to the surface of the transfer object can be reduced by the point contact state formed by the porous material.
  • the temperature on the transferred object side at the time of transfer can be set to a lower temperature (300 ° C. or lower) than the conventional one.
  • the purity of the metal powder to be sintered and the metal of the particle size are specified in consideration of the conductivity when it is used as a bump after transfer. That is, if the purity is less than 99.9% by weight, the necessary electrical conductivity may not be ensured.
  • the particle size of the metal powder a metal powder having a particle size exceeding 1.0 ⁇ m is likely to cause a large gap in the molded body, and finally necessary electric conductivity cannot be ensured.
  • the particle size of the metal powder is fine, but a powder having a particle size of less than 0.01 ⁇ m is inferior in handleability, so 0.01 ⁇ m is the lower limit.
  • the metal wiring material made of this sintered body is porous, but the density is preferably 0.45 to 0.95 times the density of the metal powder. As the sintering proceeds, the metal wiring material becomes dense, and its density approximates the density of the bulk metal. Since the metal wiring material exceeding 0.95 times the density of the bulk metal is too hard, transfer becomes difficult. On the other hand, when it is less than 0.45 times that of the bulk metal, the contact between the metal powders becomes insufficient and the conductivity is poor, which is not preferable as a metal wiring.
  • the metal wiring material is composed of gold powder, silver powder, platinum powder, palladium powder, copper powder, or an alloy powder of these metals. This is in consideration of the conductivity as a bump.
  • the metal wiring material may be obtained by sintering only one kind of these metal powders, or may be a mixture of two or more kinds.
  • gold powder may be sintered alone, it may be sintered by mixing gold powder and palladium powder, mixing gold powder and silver powder, or the like.
  • the metal wiring material is not directly formed on the substrate, and a base metal film is formed between the substrate and the metal wiring material.
  • a glass substrate is often used as the substrate. However, glass has poor bondability with metal, and if a metal wiring material is directly formed, it may fall off when handling a transfer substrate. Therefore, a base metal film is formed to ensure adhesion of the metal wiring material.
  • the base metal film is made of any metal of gold, silver, platinum, palladium, ruthenium, rhodium, iridium, chromium, titanium, tungsten, tantalum, nickel, copper, zirconium, or an alloy thereof.
  • At least one coating layer made of a predetermined metal may be further formed on the surface of the metal wiring material (end surface on the transfer object side).
  • a metallization process is performed on the terminal electrode on the wafer to form a barrier metal layer, and the bump is formed thereon.
  • the barrier metal layer and the bump can be formed simultaneously by forming a coating layer on the metal wiring material to be the bump in advance and performing transfer in this state.
  • the metallization process for forming the barrier layer also becomes a load on the semiconductor circuit, the provision of the coating layer makes the wafer metallization process unnecessary and reduces the load. Further, the use of the coating layer can simplify the bump forming process.
  • the metal wiring material can be transferred even if the coating layer is formed, as long as the coating layer has a predetermined thickness, the ease of joining by point contact on the surface of the sintered body described above. It is because it can maintain.
  • the thickness of the coating layer that can maintain the surface state of the sintered body needs to be 1 ⁇ m or less. However, it is more preferable if the coating layer is thin, but if it is too thin, it is difficult to ensure continuity as a metal film. Therefore, the lower limit value of the coating layer thickness is preferably 0.003 ⁇ m.
  • the metal constituting the coating layer is any metal or alloy of gold, silver, platinum, palladium, ruthenium, rhodium, iridium, chromium, titanium, tungsten, tantalum, nickel, copper, and zirconium, which is different from the metal wiring material.
  • the structure of the coating layer is preferably a dense thin film. In any form, the thickness may be 1 ⁇ m or less. Moreover, although it may be a single layer, it may be a multilayer structure made of a plurality of metals, and the total thickness may be 1 ⁇ m or less.
  • the base metal film may be a metal having the same composition as that of the metal wiring material, but is more preferably a metal film having a different composition. If the composition is the same as that of the metal wiring material, the adhesion between the metal wiring material and the underlying metal film is increased, and the metal wiring material may remain on the substrate during transfer to the transfer object. However, even if the underlying metal film and the metal wiring material have the same composition, it is possible to increase the adhesion between the metal wiring material and the transferred object by adjusting the heating conditions during transfer, etc. Since it is possible, it is not always required to have a different composition.
  • the base metal film preferably has a thickness of 1 to 100 nm. If the thickness is less than 1 nm, the adhesion between the base metal film and the substrate is low, and the adhesion of the metal wiring material cannot be ensured.
  • the upper limit is not particularly limited, but there is no difference in effect even when the thickness exceeds 100 nm.
  • the transfer rate of the metal wiring material can be adjusted by adjusting the thickness of the base metal film within the above range.
  • the base metal film and the metal wiring material are the same material (for example, when Au is used as the base metal film and Au powder is used as the metal wiring material on the glass substrate), the base metal film and the metal wiring material Since the adhesion becomes high, the base metal film can be peeled from the substrate at the time of transfer by reducing the thickness of the base metal film.
  • This method of thinning the base metal film and peeling it off at the time of transfer is more effective in adjusting the transfer rate because there are cases where the remaining metal wiring material can be suppressed as compared with the case where the base metal film is thickened.
  • the thickness is preferably 1/3 or less of the average particle diameter of the metal powder constituting the metal wiring material.
  • the base metal film may be a single layer or a plurality of layers.
  • a titanium film may be formed on a glass substrate, and a gold film may be formed thereon.
  • Such a multilayer film may be heat-treated to diffuse titanium to the outermost surface and oxidize it to form an oxide.
  • the surface oxide film may be stabilized by oxygen plasma treatment on the surface thereof.
  • This oxygen plasma treatment is a plasma treatment under atmospheric pressure or reduced pressure in ozone or an oxygen atmosphere.
  • the substrate on which the metal wiring material is formed is generally made of glass or glass reinforced with resin, but other metals such as silicon and kovar are also applicable.
  • the thickness is not particularly limited, but is preferably 50 to 500 ⁇ m in consideration of handling properties and transfer stability.
  • a base metal film is formed on a substrate such as glass, and then a metal wiring material is formed.
  • Various thin film manufacturing processes such as sputtering, plating, and CVD can be applied to the formation of the base metal film.
  • the metal wiring material is formed by sintering metal powder.
  • a metal paste in which an organic solvent is appropriately added to the metal powder. This is because the paste can be applied by various methods as will be described later, and can cope with the miniaturization of wiring.
  • ester alcohol terpineol, pine oil, butyl carbitol acetate, butyl carbitol and carbitol are preferable.
  • 2,2,4-trimethyl-3-hydroxypentaisobutyrate (C 12 H 24 O 3 ) can be given as a preferred ester alcohol organic solvent. This is because the present solvent can be dried at a relatively low temperature.
  • the metal paste may contain one or more selected from acrylic resins, cellulose resins, and alkyd resins.
  • acrylic resins include a methyl methacrylate polymer
  • examples of the cellulose resin include ethyl cellulose
  • examples of the alkyd resin include a phthalic anhydride resin. Of these, ethyl cellulose is particularly preferable.
  • the metal paste application process is not particularly limited.
  • a bump-shaped mold may be placed on the substrate and filled with the metal paste.
  • a resist may be used as in the case of bump formation by a conventional plating method.
  • various methods such as a spin coating method, a screen printing method, an ink jet method, and a method of filling the dropped paste with a spatula made of silicon rubber can be used.
  • the sintering temperature is preferably 80 to 300 ° C. This is because point contact does not occur below 80 ° C.
  • sintering is performed at a temperature exceeding 300 ° C., the sintering proceeds excessively, necking between the metal powders proceeds and is firmly bonded, and becomes too hard. Further, heating exceeding 300 ° C. may cause deformation of the glass substrate.
  • the heating time during sintering is preferably 30 to 120 minutes.
  • this sintering is preferably performed in a state where no pressure is applied.
  • the thin film-like coating layer is applied to various thin film manufacturing processes such as sputtering, plating, and CVD as with the base metal. it can.
  • the method for forming the metal wiring on the transfer object by the transfer substrate according to the present invention is basically the same as that by the conventional transfer method. That is, the transfer substrate is overlapped with the surface on which the metal wiring material is formed facing the transfer object (wafer), the transfer substrate and the transfer object are heated, and the metal wiring material is pressed against the transfer object, After the metal wiring material is bonded to the transfer object, the transfer substrate is removed. At this time, in the present invention, the heating temperature of the transfer substrate is set to 80 to 200 ° C., and the heating temperature of the transfer object is set to 80 to 300 ° C.
  • the heating temperature of the transfer object can be 80 to 300 ° C., which is lower than the transfer process using the conventional transfer substrate.
  • the heating temperature of the transfer object is preferably 100 to 200 ° C. This is to reliably transfer the metal wiring material from the transfer substrate and to effectively prevent overheating due to heat conduction from the transfer object to the transfer substrate.
  • the heating temperature of the transfer substrate is more preferably 100 to 200 ° C.
  • this pressure is preferably set to be equal to or lower than the yield strength of the metal wiring material. This is because pressurization that greatly exceeds the yield strength deforms the metal wiring material and cannot secure a predetermined height and shape.
  • the applied pressure is preferably 0.1 to 1.5 times the yield strength of the metal wiring material.
  • an electrode film made of a metal including a metal constituting the metal wiring material of the transfer substrate is formed in advance on the portion to be transferred on a portion where the metal wiring is to be formed. This is to transfer the metal wiring material reliably.
  • the electrode film on the transfer object may be made of gold.
  • the electrode film may be a single layer or a plurality of layers, and the outermost surface only needs to be made of a metal similar to the metal wiring material.
  • the transfer substrate according to the present invention can transfer the metal wiring material stably even when the heating temperature of the transfer object during transfer is low. Thereby, deformation due to overheating of the transfer substrate can be prevented, and damage to the transfer object can also be prevented.
  • a transfer substrate was manufactured using a glass substrate, and metal wiring was formed on a Si wafer using this substrate.
  • Pt was formed by sputtering as a base metal film on a glass substrate (diameter 100 mm, 4 inches, average thickness 500 ⁇ m).
  • the glass substrate was cleaned by reverse sputtering (Ar pressure 2.8 ⁇ 10 ⁇ 1 Pa, RF output 250 W, sputtering time 60 seconds), and then Ar pressure 7.0 ⁇ 10 ⁇ 1 was used using a Pt target.
  • a film was formed under the conditions of Pa, DC output of 500 W, and sputtering time of 115 seconds to form a Pt film having a thickness of 20 nm.
  • a metal wiring material was formed on the glass substrate using a metal paste made of Au powder.
  • the metal paste used here is a gold powder (average particle size: 0.3 ⁇ m) with a purity of 99.95% by weight produced by a wet reduction method, and ester alcohol (2,2,4-trimethyl-3-methyl) as an organic solvent. It is prepared by mixing hydroxypentaisobutyrate (C 12 H 24 O 3 )).
  • a photoresist was applied to a glass substrate, and a plurality of through holes were formed using a normal photolithography technique. Then, a metal paste was dropped on the surface of the photoresist, and the gold paste was filled into the through holes of the photoresist by a spin coating method.
  • coating was dried with the dryer hold
  • the substrate was placed in an electric furnace to sinter the gold powder to form a metal wiring material.
  • the sintering temperature was heated at 90 ° C. for 1 hour.
  • 100 rectangular metal wiring materials (diameter size 50 ⁇ m, height 25 ⁇ m) are formed on the substrate at equal intervals.
  • FIG. 1 is a diagram for explaining the process.
  • the transfer glass substrate manufactured in this embodiment is placed on the upper heating block by suction, and an Si wafer (size 100 mm, 4 inches) for forming wiring is placed on the lower heating block.
  • Ti / Pt / Au thickness 50 nm / 50 nm / 200 nm is formed as an electrode film.
  • the upper heating block is lowered to bring the transfer substrate into close contact with the Si wafer.
  • the upper heating block was heated to 150 ° C.
  • the lower heating block was heated to 150 ° C.
  • the upper heating block was pressed at a pressure of 30 MPa, and this pressed state was maintained for 10 minutes.
  • the upper heating block was raised.
  • the applied pressure at this time is set to 1.4 times the yield strength (21 MPa) of the gold powder sintered body measured in advance at 150 ° C. or lower.
  • the remaining metal wiring material on the transfer substrate was confirmed, but there was no transfer residue, and all the metal wiring material was transferred onto the Si wafer, confirming the formation of the metal wiring. . Further, the individual height of the transferred metal wiring was measured and the variation was confirmed, but it was confirmed that it was within a range of ⁇ 0.5 ⁇ m and the shape was good.
  • a metal substrate (metal paste) constituting a metal wiring material on a transfer substrate and a base metal film are variously modified to produce a transfer substrate, and each is used to manufacture a Si wafer. Metal wiring was formed.
  • the structure of the manufactured transfer substrate is as follows. The manufacturing conditions of these transfer substrates are the same as those in the first embodiment except for the type of metal powder and the target material for forming the base metal (when the base metal film is an alloy, an alloy target having the same composition is used). It is the same.
  • the metal wiring was formed on the Si wafer using the above various transfer substrates. For these tests, the metal film on the Si wafer is partially changed. In addition, the heating temperature of the lower block is partially changed. The test results are shown in Table 2.
  • the transfer substrate is manufactured by variously changing the configuration of the coating layer, and each is used. Then, metal wiring was formed on the Si wafer.
  • the production conditions of the transfer substrate are basically the first implementation, using the type of metal powder and the target material for forming the base metal (when the base metal film is an alloy, an alloy target having the same composition is used). A process similar to that of the form was followed.
  • the coating layer was formed by coating and drying the metal paste, forming a coating layer thereon, and then removing the resist to sinter the metal powder.
  • the coating layer was formed by a plating method under the conditions recommended using a commercially available plating solution as appropriate. Moreover, the coating layer can also be formed by a sputtering method, and a commercially available sputtering target material was also used.
  • the structure of the manufactured transfer substrate is as follows.
  • FIG. 2 is a diagram for explaining the process. The test results are shown in Table 4.
  • the present invention can provide a processing process at a temperature lower than that in the prior art in forming metal wiring on an object to be transferred such as a semiconductor wafer, a compound wafer, and a MEMS wafer, and contributes to miniaturization of metal wiring and quality maintenance. be able to.

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Abstract

　本発明は、基板と、前記基板上に形成された少なくとも一つの金属配線素材と、前記基板と前記金属配線素材との間に形成された下地金属膜とからなり、前記金属配線素材を被転写物に転写させるための転写用基板であって、前記金属配線素材は、純度９９．９重量％以上、平均粒径０．０１μｍ～１．０μｍである金粉等を焼結してなる成形体であり、前記下地金属膜は、金等の金属又は合金等からなる転写用基板である。この転写用基板は、被転写物の加熱温度を８０～３００℃としても金属配線素材を被転写物に転写することができる。

Description

金属配線形成用の転写基板及び前記転写用基板による金属配線の形成方法
　本発明は、半導体ウェハ、化合物ウェハ、ＭＥＭＳウェハ等の被転写物上へ金属配線を形成するための転写用基板及びこれを利用する金属配線方法に関する。
　半導体チップ等の電子部品の実装密度の高密度化に伴い、その実装方法は旧来のワイヤボンディング法から、フリップチップボンディング法のような回路基板に半導体チップを直付けするワイヤレス実装法が主流となってきている。この実装方法を用いる電子部品の製造工程は、デバイスウェハの半導体チップ上の端子電極又は半導体チップへの接続用外部電極にバンプを形成して金属配線を構成し、これを基板上へフェイスダウンボンディングするものである。また、バンプの形成の前には、端子電極等の上にメタライズ処理を施してバリアメタル層を形成し、その上にバンプ形成されるのが一般的である。
　バンプ形成工程の従来の方法としては、めっき法を用いるものが一般的であった。めっき法により形成されるバンプは、緻密で良好な電気伝導特性を有することから電極として有用であると考えられている。しかしながら、めっき法によるバンプ形成は、今後より進行すると考えられる金属配線の微細化に十分に対応できないとの懸念がある。そこで、特許文献１のような転写基板を用いた転写法によるバンプ形成法が提案されている。
　転写基板によるバンプ形成法では、予めガラス等の基板にバンプとなる配線素材を形成した転写用基板を作製する。そして、予めメタライズ処理されたウェハに転写基板を被せて加圧、加熱し、配線素材をウェハに転写させバンプを形成する方法である。この方法は、加圧、加熱の制御により転写用基板上の任意の配線素材を、ウェハの任意の位置に転写することができ、金属配線の微細化を可能とすると共に、ウェハ上の不良セクタへの配線形成を回避することができ素材の無駄も回避することができる。
特開平５－１４４８７０号公報
　ところで、上記の転写基板を用いるバンプ形成の過程では、転写用基板からウェハへのバンプの転写の際、ウェハ側の加熱温度と転写基板側の加熱温度に比較的温度差がある。具体的には、ウェハ側の加熱温度は３００～４００℃としつつ、転写基板側の加熱温度は１００～２００℃としている。そして、この設定温度及び温度差が転写基板の変形（そり）の要因となる。即ち、転写基板はガラスが適用されることが多く、その加熱温度が２００℃を超えると変形のおそれがある。このとき、転写基板の加熱温度自体を多少低く設定しても、ウェハ側の加熱温度が高いとバンプを介した伝熱によりガラス基板の温度上昇が懸念される。
　また、バンプの転写のためにウェハ側の温度を高温にすることは、ウェハ上に半導体回路が形成されている場合において、回路へのダメージが懸念される。よって、本来、バンプ転写時の加熱温度は低い方が好ましいのであるが、ウェハ側の加熱温度を安易に下げることはできない。これは、転写用基板上のバンプは、一般にめっき法で形成されるが、めっきで形成されるバンプをウェハに転写させるためには、ウェハとバンプとの間に十分な接合を生させる必要があり、そのためには高温加熱が必要だからである。
　そこで本発明は、転写法によりウェハ等の被転写物上に金属配線を形成するための転写用基板について、被転写物側の加熱温度を従来よりも低くすることのできるものを提供する。また、この転写用基板を用いた、金属配線の形成方法についても開示する。
　本発明者等は、上記課題を解決すべく、被転写物に対して低温でも転写可能となる構成を有する金属配線素材を備える転写用基板を見出すべく、本発明者等の有する技術的知見を考慮して検討を行った。そして、高純度であり、微細粒径の金属粉末を焼結してなる成形体は、比較的低温でも被転写物に接合可能であること、及び、それが金属配線として機能することを見出し本発明に想到した。
　即ち、本発明は、基板と、前記基板上に形成された少なくとも一つの金属配線素材と、前記基板と前記金属配線素材との間に形成された下地金属膜とからなり、前記金属配線素材を被転写物に転写させるための転写用基板であって、前記金属配線素材は、純度９９．９重量％以上、平均粒径０．０１μｍ～１．０μｍである金粉、銀粉、白金粉、パラジウム粉、銅粉から選択される一種以上の金属粉末を焼結してなる成形体であり、前記下地金属膜は、金、銀、白金、パラジウム、ルテニウム、ロジウム、イリジウム、クロム、チタン、タングステン、タンタル、ニッケル、銅、ジルコニウムの何れかの金属又はこれらの合金からなる転写用基板である。
　以下、本発明につき詳細に説明する。上記の通り、本発明に係る転写用基板は、被転写物（ウェハ）に転写させる金属配線素材（バンプ）として、所定の金属粉末を焼結して形成した焼結体を適用することを特徴とする。この焼結体からなる金属配線素材は、従来技術のめっきにより形成される緻密なものとは相違して多孔質であり、転写時において被転写物表面と点接触で接する。本発明者等によれば、この多孔質が形成する点接触状態により、被転写物面との接合に要する温度を低減することができると考える。そして、これにより転写時の被転写物側の温度を従来よりも低い温度（３００℃以下）にすることができる。
　この焼結体からなる金属配線素材について、焼結する金属粉末の純度、粒径の金属を規定するのは、純度については、転写後のバンプとしたときの導電性を考慮するものである。つまり、純度が９９．９重量％未満であると必要な通電性を確保できないおそれがあるからである。また、金属粉末の粒径については、１．０μｍを超える粒径の金属粉では、成形体に大きな隙間が生じ易くなり、最終的に必要な通電性を確保できないからである。尚、金属粉末の粒径は細かいことが好ましいが０．０１μｍ未満の粒径の粉末は取扱い性に劣ることから、０．０１μｍを下限とする。
　この焼結体からなる金属配線素材は、多孔質であるが、その密度は金属粉の密度の０.４５～０．９５倍となっているものが好ましい。焼結を進行させると金属配線素材は緻密なものとなり、その密度はバルク体である金属の密度に近似する。バルク金属の密度の０．９５倍を超える金属配線素材は硬すぎるため、転写が困難となる。一方、バルク金属の０．４５倍未満となると、金属粉同士の接触が不十分となり導電性に乏しく、金属配線として好ましくない。
　また、金属配線素材は金粉、銀粉、白金粉、パラジウム粉、銅粉、又は、これら金属の合金粉より構成させる。バンプとしての導電性を考慮したものである。金属配線素材は、これらの金属粉末の１種類のみを焼結したものでも良いが、２種以上を混合しても良い。例えば、金粉を単独で焼結しても良いが、金粉とパラジウム粉とを混合する、金粉と銀粉とを混合する等してこれを焼結しても良い。
　そして、上記金属配線素材は、基板に直接形成されることはなく、基板と金属配線素材との間には、下地金属膜が形成される。基板にはガラス基板を用いることが多くなるが、ガラスは金属との接合性に乏しく、直接金属配線素材を形成すると、転写用基板の取扱い時に脱落するおそれがある。そこで、金属配線素材の密着性確保のため下地金属膜を形成する。この下地金属膜は、金、銀、白金、パラジウム、ルテニウム、ロジウム、イリジウム、クロム、チタン、タングステン、タンタル、ニッケル、銅、ジルコニウムの何れかの金属又はこれらの合金からなる。
　本発明に係る転写用基板は、更に、金属配線素材の表面上（被転写物側の端面）に所定の金属からなる被覆層を少なくとも１層形成しても良い。上記の通り、ワイヤレス実装法による電子部品の製造工程においては、バンプの形成の前に、ウエハ上の端子電極等の上にメタライズ処理を施してバリアメタル層を形成し、その上にバンプ形成されること多い。そこで、本発明では、バンプとなる金属配線素材の上にあらかじめ被覆層を形成し、この状態で転写を行うことで、バリアメタル層とバンプを同時に形成することができる。バリア層形成のためのメタライズ処理も半導体回路にとっては負荷となるが、被覆層を設けることによりウェハのメタライズ処理を不要としそれによる負荷を軽減することができる。また、被覆層の利用は、バンプ形成の工程を簡略化することができる。
　このように、被覆層が形成されていても金属配線素材の転写が可能であるのは、被覆層が所定の厚さであれば、上述した焼結体の表面の点接触による接合の容易性を維持することができるからである。ここで、焼結体の表面状態が維持できる程度の被覆層の厚さとしては、１μｍ以下にすることを要する。但し、被覆層は薄ければより好ましいといえるが、あまりに薄いと金属膜としての連続性を確保するのが困難となる。そこで、被覆層厚さの下限値としては０．００３μｍとするのが好ましい。
　被覆層を構成する金属は、金、銀、白金、パラジウム、ルテニウム、ロジウム、イリジウム、クロム、チタン、タングステン、タンタル、ニッケル、銅、ジルコニウムの何れかの金属又は合金であり、金属配線素材と相違する金属である。また、被覆層の構造は、緻密質の薄膜状のものが好ましい。いずれの形態であっても１μｍ以下の厚さであれば良い。また、単層であっても良いが、複数の金属による多層構造であっても良く、合計の厚さが１μｍ以下であれば良い。
　この下地金属膜は、金属配線素材と同じ組成の金属であっても良いが、相違する組成の金属膜であることがより好ましい。金属配線素材と同一の組成とすると、金属配線素材と下地金属膜との密着性が高くなり、被転写物への転写時に金属配線素材が基板に残留するおそれがある。但し、下地金属膜と金属配線素材とを同一の組成で構成しても、転写時の加熱条件の調整等により金属配線素材と被転写物との密着性を高くし、残留を回避することができることから、必ずしも組成を異にすることが要求されるものではない。
　下地金属膜は、厚さ１～１００ｎｍとするのが好ましい。１ｎｍ未満では、下地金属膜と基板との密着性が低く、金属配線素材の密着性を確保することができない。また、上限については特に制限はないが、１００ｎｍを超える厚さにしても効果に相違はない。そして、上記の範囲内で下地金属膜の厚さを調整することで、金属配線素材の転写率の調整を行うことができる。これは、下地金属膜と金属配線素材とが同じ材質の場合（例えば、ガラス基板に下地金属膜としてＡｕを、金属配線素材としてＡｕ粉末を用いた場合）、下地金属膜と金属配線素材との密着性が高くなるため、下地金属膜の厚さを薄くすることで、転写時に下地金属膜を基板から剥離させることができる。この下地金属膜を薄くして、転写時に剥離させる方法は、下地金属膜を厚くする場合よりも、金属配線素材の残留を抑制することができる場合があるため効果的な転写率の調整となる。このように転写時の剥離を狙って下地金属膜を薄くする場合、その厚さは金属配線素材を構成する金属粉末の平均粒子径の１／３以下とするのが好ましい。
　下地金属膜は、単層でも良いが複数層形成しても良い。例えば、ガラス基板にチタン膜を形成し、その上に金膜を形成しても良い。このような多層膜を熱処理してチタンを最表面に拡散させると共に酸化させ酸化物を形成しても良い。
　尚、Ｃｒ、Ｗ、ＴｉＷ等は酸化し易い金属であり、これらを単層で用いる場合、その表面を酸素プラズマ処理して表面酸化膜を安定化させておいても良い。この酸素プラズマ処理とは、オゾンや酸素雰囲気中での大気圧又は減圧下のプラズマ処理である。
　金属配線素材を形成する基板は、材質としては、ガラス或いは樹脂補強されたガラスが一般的であるが、その他、シリコン、コバール等の金属も適用できる。また、その厚さも特に制限はないが、取扱い性や転写の安定性を考慮して５０～５００μｍとするのが好ましい。
　本発明に係る転写用基板の製造工程としては、ガラス等の基板に対し、下地金属膜を形成し、その後金属配線素材の形成を行う。下地金属膜の形成は、スパッタリング法、めっき法、ＣＶＤ法等の各種の薄膜製造プロセスが適用できる。
　一方、金属配線素材の形成について、これまで述べたように、本発明においては、金属粉を焼結して金属配線素材を形成する。この金属粉からなる金属配線素材の形成にあたっては、金属粉に適宜に有機溶剤を添加した金属ペーストを用いて成形することが好ましい。ペーストは、後述するように多様な方法で塗布可能であり、また、配線の微細化にも対応できるからである。
　金属ペーストの有機溶剤としては、エステルアルコール、ターピネオール、パインオイル、ブチルカルビトールアセテート、ブチルカルビトール、カルビトールが好ましい。例えば、好ましいエステルアルコール系の有機溶剤として、２，２，４－トリメチル－３－ヒドロキシペンタイソブチレート（Ｃ１２Ｈ２４Ｏ３）を挙げることができる。本溶剤は、比較的低温で乾燥させることができるからである。
　また、上記有機溶剤に加えて、金属ペーストは、アクリル系樹脂、セルロース系樹脂、アルキッド樹脂から選択される一種以上を含有していても良い。これらの樹脂等を更に加えると金属ペースト中の金属粉の凝集が防止されてより均質となり、偏りのないバンプが形成できる。尚、アクリル系樹脂としては、メタクリル酸メチル重合体を、セルロース系樹脂としては、エチルセルロースを、アルキッド樹脂としては、無水フタル酸樹脂を、それぞれ挙げることができる。そして、これらの中でも特にエチルセルロースが好ましい。
　金属ペーストの塗布工程は特に限られるものはなく、例えば、バンプ形状の型を基板上に載置し、これに金属ペーストを充填しても良い。また、従来のめっき法によるバンプ形成と同様、レジストを使用しても良い。金属ペーストの塗布方法としては、スピンコート法、スクリーン印刷法、インクジェット法、滴下したペーストをシリコンゴム製のへらで広げることで孔内に充填する方法等、種々の方法を用いることができる。
　金属ペースト塗布後は、金属ペーストを塗布・乾燥した後に焼結することを要する。これにより、ペースト中の金属粒子どうし、及び接合部材の接合面（ペースト塗布面）と金属粒子との間に、互いに点接触した近接状態が形成され、金属配線素材としての形状が安定する。この焼結の温度は、８０～３００℃とするのが好ましい。８０℃未満では点接触が生じないからである。一方、３００℃を超える温度で焼結すると、焼結が過度に進行し、金属粉末間のネッキングが進行して強固に結合し、硬すぎる状態となるからである。また、３００℃を超える加熱はガラス基板の変形が生じる恐れがある。尚、焼結の際の加熱時間は、３０～１２０分とするのが好ましい。短時間では焼結炉の温度が安定せず十分な焼結ができず、また、あまりに長時間とすると生産性が損なわれるからである。また、この焼結は、圧力の負荷のない状態で行なうのが好ましい。
　また、金属配線素材上に被覆層を形成する場合、その形成方法は、薄膜状の被覆層については、下地金属と同様に、スパッタリング法、めっき法、ＣＶＤ法等の各種の薄膜製造プロセスが適用できる。
　次に本発明に係る転写用基板による被転写物への金属配線の形成方法は、基本的には従来の転写法によるものと同一である。即ち、転写用基板を金属配線素材が形成された面が被転写物（ウェハ）に対向した状態で重ね、転写用基板及び被転写物を加熱すると共に金属配線素材を被転写物に押圧し、金属配線素材を被転写物に接合させた後に、転写用基板を除去するものである。このとき本発明においては、転写用基板の加熱温度を８０～２００℃とし、被転写物の加熱温度を８０～３００℃とするものである。
　本発明では、被転写物の加熱温度を８０～３００℃と従来の転写基板による転写工程よりも低温とすることができる。そして、この被転写物の加熱温度については、好ましくは１００～２００℃とする。転写用基板からの金属配線素材を確実に転写させるため、そして、被転写物から転写基板への熱伝導による過熱を効果的に防ぐためである。また、転写用基板の加熱温度としては、１００～２００℃とするのがより好ましい。
　また、この転写法では金属配線素材の被転写物への押圧即ち加圧が必要であるが、この圧力は、金属配線素材の降伏強度以下とすることが好ましい。降伏強度を大きく超えた加圧は金属配線素材を変形させ、所定の高さや形状を確保できないからである。具体的には、金属配線素材の降伏強度に対して０．１～１．５倍の加圧力とすることが好ましい。
　尚、被転写物には、金属配線を形成する部位に、予め、転写用基板の金属配線素材を構成する金属を含む金属からなる電極膜を形成するのが好ましい。確実に金属配線素材を転写させるためである。但し、完全な同一組成とする必要はない。例えば、金属配線素材が金粉と銀粉との混合体からなる場合、被転写物への電極膜を金で構成すれば良い。また、この電極膜は、単層でも複数層でも良く、最表面が金属配線素材と同系の金属からなっていれば良い。
　以上説明したように、本発明に係る転写用基板は、転写時の被転写物の加熱温度を低温としても安定的に金属配線素材を転写させることができる。これにより、転写基板の過熱による変形を防ぐことができ、また、被転写物の損傷も防止できる。
第１実施形態における金属配線の形成工程を概略説明する図。 第３実施形態における金属配線の形成工程を概略説明する図。
第１実施形態：ガラス基板を用いて転写用基板を製造し、これを用いてＳｉウェハーへの金属配線形成を行った。
（転写用基板の製造）
　まず、ガラス基板（直径寸法１００mm、４インチ、平均厚さ５００μｍ）に下地金属膜としてＰｔをスパッタリングにより成膜した。Ｐｔ膜形成は、逆スパッタ（Ａｒ圧力２．８×１０－１Ｐａ、ＲＦ出力２５０Ｗ、スパッタ時間６０秒）でガラス基板をクリーニングした後、Ｐｔターゲットを用いてＡｒ圧力７．０×１０－１Ｐａ、ＤＣ出力５００Ｗ、スパッタ時間１１５秒の条件で成膜し、厚さ２０ｎｍのＰｔ膜を形成した。
　次に、Ａｕ粉末からなる金属ペーストを用いて、ガラス基板上に金属配線素材を形成した。ここで使用した金属ペーストは、湿式還元法により製造された純度９９．９５重量％の金粉（平均粒径：０．３μｍ）と、有機溶剤としてエステルアルコール（２，２，４－トリメチル－３－ヒドロキシペンタイソブチレート（Ｃ１２Ｈ２４Ｏ３））を混合して調整されたものである。金属配線素材の形成にあたっては、ガラス基板にフォトレジストを塗布し、通常のフォトリソグラフ技術を用いて複数の貫通孔を形成した。そして、金属ペーストをフォトレジストの表面に滴下し、スピンコート法によってフォトレジストの貫通孔内に金ペーストを充填した。次に、ペースト塗布後の基板を５０℃以下の温度で保持された乾燥器にて乾燥し、その後レジストを有機溶剤で剥離した。レジスト剥離後、基板を電気炉に入れて金粉末を焼結させて金属配線素材を形成した。焼結温度は９０℃で１時間加熱した。本実施形態では、基板上に矩形の金属配線素材（直径寸法５０μｍ、高さ２５μｍ）を等間隔に１００個形成した。
（ウェハーへの転写）
　上記で製造した転写用基板を用いて、Ｓｉウェハへの配線形成を行った。図１は、その工程を説明する図である。図１のように、本実施形態で製造した転写用ガラス基板を上部加熱ブロックに吸着設置し、配線を形成するＳｉウェハ（寸法１００mm、４インチ）を下部加熱ブロックに設置する。Ｓｉウェハの表面には、電極膜としてＴｉ／Ｐｔ／Ａｕ（厚さ５０ｎｍ／５０ｎｍ／２００ｎｍ）が形成されている。転写用基板及びＳｉウェハの設置後、上部加熱ブロックを下降させ、転写用基板をＳｉウェハに密着させる。そして、上部加熱ブロックを１５０℃、下部加熱ブロックを１５０℃に加熱し、加圧力３０ＭＰａで上部加熱ブロックを押圧し、この押圧状態を１０分間維持した。時間経過後、上部加熱ブロックを上昇させた。尚、このときの加圧力は、予め１５０℃以下で測定した金粉末焼結体の降伏強度（２１ＭＰａ）の１．４倍に設定している。
　上部加熱ブロック上昇後、転写用基板の金属配線素材の残存を確認したが、転写残りは存在せず、Ｓｉウェハ上に全ての金属配線素材が転写されており、金属配線の形成が確認された。また、転写された金属配線について、その個々の高さを測定し、ばらつきを確認したが、±０．５μｍの範囲内にあり、その形状も良好であることが確認された。
第２実施形態：ここでは、転写基板上の金属配線素材を構成する金属粉末（金属ペースト）、下地金属膜の構成を種々変更して転写用基板を製造し、それぞれを用いてＳｉウェハへの金属配線形成を行った。ここで、製造した転写用基板の構成は以下の通りである。これらの転写用基板の製造条件は、金属粉末の種類及び下地金属形成のためのターゲット材質（下地金属膜が合金の場合は、同一組成の合金ターゲットを使用した）以外は、第１実施形態と同様である。
Figure JPOXMLDOC01-appb-T000001
　上記の各種転写用基板を用いて、Ｓｉウェハへの金属配線形成を行った。これらの試験については、Ｓｉウェハ上の金属膜を一部変更している。また、下部ブロックの加熱温度も一部変更している。この試験結果を表２に示す。
Figure JPOXMLDOC01-appb-T000002
　上記表２からわかるように、金属配線素材を各種の金属粉末で形成した場合、或いは、下地金属膜を変更した場合のいずれにおいても３００℃以下の低温で確実な転写が可能であることがわかる。但し、いくら低温であってもウェハ側の加熱温度が低い場合には転写率が悪化する傾向がある（試験Ｎｏ．１８）。また、粒径の粗い金属粉末を用いた場合（試験Ｎｏ．１９）、ウェハ側の加熱温度を比較的高めにしても、転写率に劣ることがわかる。
第３実施形態：ここでは、転写基板上の金属配線素材を構成する金属粉末（金属ペースト）、下地金属膜に加え、被覆層の構成を種々変更して転写用基板を製造し、それぞれを用いてＳｉウェハへの金属配線形成を行った。転写用基板の製造条件は、金属粉末の種類及び下地金属形成のためのターゲット材質（下地金属膜が合金の場合は、同一組成の合金ターゲットを使用した）を使用し、基本的に第１実施形態と同様の工程に従った。被覆層の形成は、第１実施形態の工程において、金属ペーストの塗布・乾燥後、その上に被覆層を形成し、その後レジスト剥離を行って金属粉末を焼結した。被覆層の形成は、めっき法による被覆層形成は、適宜に市販のめっき液を用いて推奨される条件で成膜した。また、被覆層をスパッタリング法で形成することもでき、これも市販のスパッタリングターゲット材を使用した。製造した転写用基板の構成は以下の通りである。
Figure JPOXMLDOC01-appb-T000003
　上記の各種転写用基板を用いて、Ｓｉウェハへの金属配線形成を行った。これらの試験については、Ｓｉウェハ上の金属膜を一部変更している。また、下部ブロックの加熱温度も一部変更している。図２は、その工程を説明する図である。この試験結果を表４に示す。
Figure JPOXMLDOC01-appb-T000004
　上記表４からわかるように、金属配線素材を各種の金属粉末で形成した場合、或いは、下地金属膜を変更した場合のいずれにおいても３００℃以下の低温で確実な転写が可能であることが確認できる。もっとも、いくら低温であってもウェハ側の加熱温度が低い場合には転写率が悪化する傾向がある（試験Ｎｏ．４８）。
　また、粒径の粗い金属粉末を用いた場合（試験Ｎｏ．４９）、ウェハ側の加熱温度を比較的高めにしても、転写率に劣ることがわかる。更に、被覆層に関してみると、厚さ１μｍを超えた場合、転写率の低下が見られる（試験Ｎｏ．５０、５１）。
第４実施形態：ここでは、第３実施形態の試料Ｎｏ．３９～５１について、第２実施形態と同様にしてバンプ形成を行い。バンプのシェア強度（接合力）を測定した。ここでの加圧力は２種（１ＭＰａ、５ＭＰａ）設定した。また、シェア強度の測定はボンディングテスタにて行った。その結果を表５に示す。
Figure JPOXMLDOC01-appb-T000005
　表５から、金粉末焼結体の降伏強度（２１ＭＰａ）を考慮すると、被覆層の厚さが１μｍを超えている場合（試験Ｎｏ．６（試料Ｎｏ．４４）と試験Ｎｏ．１０(試料Ｎｏ．４８)）、シェア強度が２０ＭＰａより小さく強度不足となっていた。そして、被覆層厚さを１μｍ以下にした試料では、いずれも良好な強度を保持していた。これは、上述のように、被覆層が厚くなると金属配線素材の表面状態を維持することができず、焼結体としての接合性が低下したためと考えられる。
　本発明は、半導体ウェハ、化合物ウェハ、ＭＥＭＳウェハ等の被転写物上への金属配線形成において、従来よりも低温の加工工程を提供することができ、金属配線の微細化、品質保持に貢献することができる。

Claims (8)

  1. 基板と、前記基板上に形成された少なくとも一つの金属配線素材と、前記基板と前記金属配線素材との間に形成された下地金属膜とからなり、前記金属配線素材を被転写物に転写させるための転写用基板であって、
    　前記金属配線素材は、純度９９．９重量％以上、平均粒径０．０１μｍ～１．０μｍである金粉、銀粉、白金粉、パラジウム粉、銅粉から選択される一種以上の金属粉末を焼結してなる成形体であり、
    　前記下地金属膜は、金、銀、白金、パラジウム、ルテニウム、ロジウム、イリジウム、クロム、チタン、タングステン、タンタル、ニッケル、銅、ジルコニウムの何れかの金属又はこれらの合金からなる転写用基板。
  2. 更に、金属配線素材の表面上に形成された少なくとも１層の被覆層を備え、
    　前記被覆層は、金、銀、白金、パラジウム、ルテニウム、ロジウム、イリジウム、クロム、チタン、タングステン、タンタル、ニッケル、銅、ジルコニウムの何れかの金属又はこれらの合金であって、前記金属配線素材と相違する組成の金属又は合金からなり、かつ、その合計厚さは１μｍ以下である請求項１記載の転写用基板。
  3. 下地金属膜は、金属配線素材と相違する組成の金属又は合金からなる請求項１又は請求項２記載の転写用基板。
  4. 下地金属膜は、厚さ１～１００ｎｍである請求項１～請求項３のいずれかに記載の転写用基板。
  5. 請求項１～請求項４のいずれかに記載の転写用基板を被転写物に対向させて重ね、前記転写用基板及び前記被転写物を加熱すると共に、前記転写用基板を押圧して金属配線素材を前記被転写物に接合して転写する金属配線の形成方法であって、
    　前記転写用基板の加熱温度を８０～２００℃とし、前記被転写物の加熱温度を８０～３００℃とする方法。
  6. 転写用基板を押圧する際の圧力を、金属配線素材の降伏強度の０．１～１．５倍とする請求項５記載の金属配線の形成方法。
  7. 被転写物に転写用基板の金属配線素材を構成する金属を含む金属からなる電極膜を形成した後、金属配線素材を転写する請求項５又は請求項６記載の金属配線の形成方法。
  8. 転写用基板の金属配線素材を、純度９９．９重量％以上、平均粒径０．０１μｍ～１．０μｍである金粉、銀粉、白金粉、パラジウム粉、銅粉から選択される一種以上の金属粉末と有機溶剤とからなる金属ペーストを塗布し、焼結して製造する請求項５～請求項７のいずれかに記載の金属配線の形成方法。
PCT/JP2011/076628 2010-11-26 2011-11-18 金属配線形成用の転写基板及び前記転写用基板による金属配線の形成方法 WO2012070480A1 (ja)

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US13/879,803 US8912088B2 (en) 2010-11-26 2011-11-18 Transfer substrate for forming metal wiring and method for forming metal wiring using said transfer substrate
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