US20100206737A1 - Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv) - Google Patents

Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv) Download PDF

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US20100206737A1
US20100206737A1 US12/372,113 US37211309A US2010206737A1 US 20100206737 A1 US20100206737 A1 US 20100206737A1 US 37211309 A US37211309 A US 37211309A US 2010206737 A1 US2010206737 A1 US 2010206737A1
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copper
wafer
tsv
tsvs
high purity
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Robert F. Preisser
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Atotech Deutschland GmbH and Co KG
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Priority to US12/372,113 priority Critical patent/US20100206737A1/en
Assigned to ATOTECH DEUTSCHLAND GMBH reassignment ATOTECH DEUTSCHLAND GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PREISSER, ROBERT F.
Priority to CN200980156992.4A priority patent/CN102318041B/zh
Priority to PCT/IB2009/007793 priority patent/WO2010094998A1/en
Priority to EP09799392.7A priority patent/EP2399281B1/en
Priority to JP2011549685A priority patent/JP5743907B2/ja
Priority to TW098144125A priority patent/TW201034120A/zh
Publication of US20100206737A1 publication Critical patent/US20100206737A1/en
Assigned to BARCLAYS BANK PLC, AS COLLATERAL AGENT reassignment BARCLAYS BANK PLC, AS COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ATOTECH DEUTSCHLAND GMBH, ATOTECH USA INC
Assigned to ATOTECH DEUTSCHLAND GMBH, ATOTECH USA, LLC reassignment ATOTECH DEUTSCHLAND GMBH RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: BARCLAYS BANK PLC, AS COLLATERAL AGENT
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    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
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    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
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    • H01L2224/056—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
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    • H01L2224/05647—Copper [Cu] as principal constituent
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Definitions

  • the invention relates to a process of electrolytically forming conductor structures from highly pure copper, more specifically to electrolytically forming conductor structures from highly pure copper in through-silicon vias (TSVs) when producing devices such as MEMS or semiconductor devices.
  • TSVs are useful, e.g., in integrated circuits, in a stacked or 3D arrangement, in which the TSV provide electrical connection between the respective layers of the device, where the TSV have relatively large diameter, relatively great depth and a high aspect ratio.
  • 3-D wafer stacking represents a wafer level packaging technique in which specific components, such as logic, memory, sensors, A/D converters, etc., are fabricated on separate wafer platforms and then integrated onto a single wafer-scaled package using Through-Silicon Vias (TSVs) to provide electrical interconnection between elements of the 3-D stack.
  • TSVs Through-Silicon Vias
  • interconnect material Although several conductive materials such as gold, polysilicon, and tin-lead (Sn-Pb) solder have been used as interconnect material, copper is the best and most preferred choice due to its higher electrical conductivity and electromigration resistance. For the purpose of depositing metal in deep through-holes, e.g., TSVs, electroplating is the most widely used process.
  • TSVs have been used for forming electrical connections between respective layers in a stacked or 3D arrangement in devices such as MEMS and semiconductor devices, but have suffered from various defects arising, at least partially, from difficulty in electroplating highly pure copper into the very large, high aspect ratio vias in the TSVs.
  • a typical TSV has an inner diameter in the range from about 1.5 to about 10 microns (although greater diameter TSVs may also be used), and a depth ranging from about 5 microns to about 450 microns or even greater depths (although wafer thicknesses of 5 to 25 microns, or of 100 microns, are more common in some applications). Future inner diameters are expected to be, for example, about 1 micron.
  • the aspect ratio (depth/width) of the typical TSV may be about 3:1 or greater, or the aspect ratio may be about 5:1, at present, or the aspect ratio may be about 10:1, and the aspect ratio may be as high as 50:1, and future aspect ratios are expected to be commonly from about 10:1 to about 20:1.
  • the internal stress problem (a) can be the most troublesome, since it results in bending and deformation of the silicon substrate through which the TSV is formed, and this can cause failure of the entire 3D arrangement. This failure may not occur until after the entire device has been fabricated, resulting in loss of not only the failed silicon substrate, but of the whole device into which it has been incorporated at the time of failure.
  • the present invention avoids the disadvantages of known processes and, more particularly, maximizes the electrodeposited filling of the TSVs with highly pure copper while at the same time the invention minimizes stress, avoids defects such as inclusions and voids, as well as other defects which have been found in prior art TSVs.
  • the invention relates to a process of electrolytically forming conductor structures from highly pure copper in through-silicon vias (TSVs) formed in silicon substrates such as silicon wafers used, e.g., in semiconductor devices.
  • TSVs through-silicon vias
  • the via includes an inner surface having an internal width dimension in the range from about 1.5 microns to about 30 microns, a depth from about 5 microns to about 450 microns and a depth:width aspect ratio of at least 3:1;
  • forming a dielectric layer on the inner surface of the via optionally, forming a dielectric layer on the inner surface of the via;
  • barrier layer over the dielectric layer, or, if no dielectric layer is present, forming the barrier layer over the inner surface of the via, wherein the barrier layer is formed of or comprises a material which inhibits or provides an ability to the barrier layer to inhibit diffusion of copper into the silicon substrate;
  • the silicon substrate immersing the silicon substrate into an electrolytic bath in an electrolytic copper plating system with the basic metal layer connected as a cathode, the system further comprising an insoluble dimensionally stable anode and a source of copper metal, wherein the electrolytic bath comprises an acid, a source of copper ions, a source of ferrous and/or ferric ions, and at least one additive for controlling physical-mechanical properties of deposited copper; and
  • the applying is effective to electrodeposit the high purity copper to completely fill the via, with no voids and no defects that inhibit its function in the finished device. In another embodiment, the applying is effective to electrodeposit the high purity copper to form a copper lining in the via of sufficient thickness to be capable of function as a TSV.
  • the deposited high purity copper is either substantially free of internal stress or includes a level of internal stress that does not result in bending of the silicon substrate upon subsequent processing.
  • the deposited copper is substantially free of voids and non-copper inclusions.
  • the basic metal layer is formed over the barrier layer by one or more of an electroless plating process, a physical deposition process, a chemical vapor deposition process, or a plasma-enhanced chemical vapor deposition process.
  • the basic metal layer has a thickness in the range from about 0.02 ⁇ m to about 0.5 ⁇ m.
  • the basic metal layer comprises copper.
  • the barrier layer comprises tantalum.
  • the dielectric layer when present, comprises silicon dioxide.
  • the barrier layer is a material which, in addition to functioning as a barrier layer, also is a dielectric material
  • the acid is sulfuric acid at a concentration in the range from about 50 to about 350 g/l
  • the source of copper ions is copper sulfate pentahydrate at a concentration in the range from about 20 to about 250 g/l
  • the source of ferrous and/or ferric ions is ferrous sulfate heptahydrate and/or ferric sulfate nonahydrate at a concentration in the range from about 1 to about 120 g/l
  • the at least one additive comprises one or more of a polymeric oxygen-containing compound, an organic sulfur compound, a thiourea compound and a polymeric phenazonium compound.
  • the electrical voltage is applied in a pulse current or a pulse voltage.
  • the electrical voltage is applied in a reverse pulse form with bipolar pulses.
  • FIG. 1 is a schematic cross-sectional view of a 3D device including a substrate having mounted thereon two wafers including copper-filled TSVs electrodeposited by a process according to an embodiment of the present invention.
  • FIGS. 2-9 are schematic cross-sectional views of steps in a process of forming TSVs in a wafer and mounting the wafer onto a substrate to form part of a 3D device such as that shown in FIG. 1 in accordance with an embodiment of the present invention.
  • FIGS. 10-12 are schematic cross-sectional views of steps in a process of forming TSVs in a wafer and mounting the wafer onto a substrate to form part of a 3D device in accordance with another embodiment of the present invention.
  • the term “high purity copper”, in reference to the copper electrodeposited in accordance with the present invention, refers to copper having a purity of at least 99%, and in one embodiment, to copper having a purity of at least 99.5%, and in another embodiment, to copper having a purity of at least 99.9%, and in yet another embodiment, to copper having a purity of at least 99.99%, as determined by standard chemical/instrumental analytical methods.
  • ICP-MS inductively coupled plasma mass spectrometry
  • the purity of the copper deposit is primarily determined by the purity of the copper raw material, in addition to the herein disclosed process and system.
  • physical-mechanical properties when applied to an electrodeposited metal layer in accordance with the present invention, refers to one or more of brightness, ductility, grain size, hardness, resistivity, contact resistance and reliability performance.
  • Formation of vias with smooth sidewalls in the silicon substrate is an important step in the fabrication of a 3D device employing TSVs.
  • a number of methods have been used, including wet etching, electrochemical etching, laser drilling and deep reactive ion etching (DRIE), and any one of them may be used in connection with the present invention.
  • DRIE deep reactive ion etching
  • it appears that DRIE is the most suitable process for forming TSVs having optimum features. DRIE creates almost vertical through-holes with relatively smooth surfaces at high etch rates.
  • DRIE is used to form the initial vias in which the TSVs are to be formed in the present invention.
  • TSVs may be created at various points in the manufacturing sequence—in the frontend wafer fab (before or after FEOL processes), or in the assembly and packaging facility after BEOL (before or after bonding). When viewed this way, the integration schemes under consideration can be classified as via-first or via-last, depending on when the vias are created.
  • the size of the TSVs varies somewhat with the timing of the via formation, since vias created at different points in the process may be for different purposes or uses. The following are exemplary sizes of TSVs for various timings of TSV formation.
  • the TSVs are relatively small, in the range from about 1 ⁇ m to about 5 ⁇ m diameter and from about 5 ⁇ m to about 50 ⁇ m depth, with high aspect ratios since these may be used for higher density interconnects.
  • the TSVs are typically somewhat larger, from about 2 ⁇ m to about 20 ⁇ m diameter and from about 10 ⁇ m to about 150 ⁇ m depths.
  • the number and density of TSVs may be very high.
  • via-last applications processing in the frontend wafer fab is complete, and the vias generally penetrate the full stack of BEOL insulators and conductors in addition to the silicon substrate.
  • the largest TSVs are created, having diameters from about 5 ⁇ m to about 50 ⁇ m and depths from about 20 ⁇ m to about 400 ⁇ m.
  • the interconnect density may be lower than for via-first applications, and may be, e.g., on the order of one hundred TSVs per die.
  • the TSVs may be smaller than via-last before bonding, but still may be larger than via-first, and may have a diameter in the range from about 2 to about 50 ⁇ m and a depth in the range from about 10 to about 150 ⁇ m.
  • the foregoing diameters and depths are approximate and exemplary only, and are likely to change significantly in the future.
  • the density of the TSVs for use in via-last after bonding may be about a hundred per die or higher.
  • the via-last after bonding TSVs may be etched from the backside of a wafer that has already been thinned.
  • the “fill” step includes a process of filling the TSVs by electrodeposition using a redox system based on iron ions, as described in more detail in the following.
  • Complete, void-free and inclusion-free filling of TSVs with high purity copper is a very important step in the manufacture of devices incorporating TSVs. Incomplete metal filling, e.g., filing including void formation or inclusion formation, in the TSVs can lead to short-circuiting and will affect the electrical performance of the overall device. Grain size of the deposited copper is very important, since grain roughness can directly affect the electrical properties such as electrical resistivity, electromigration resistance, and internal stress in the TSV. As noted herein, the internal stress in the TSV can result in severe problems if it causes bending or deformation of the wafer or silicon substrate through which the TSV is formed.
  • the stress can result from, e.g., rough grains or other defects, and the resulting deformation or bending can cause mechanical failure of the overall device.
  • obtaining smooth, void-free, inclusion-free, fine grain metal deposition in the high aspect ratio TSVs is essential.
  • the present invention provides such deposits of high purity copper.
  • a process of producing a highly pure copper fill in through-silicon vias (TSVs) formed, e.g., through semiconductor substrates (wafers), is provided and may be carried out.
  • TSVs through-silicon vias
  • the process provides for electrodepositing high purity copper in a via in a silicon substrate to form a through-silicon-via (TSV), including the following steps (1)-(6), (noting that step (2) is optional, as described below):
  • the via includes an inner surface having an internal width dimension in the range from about 1.5 microns to about 30 microns, a depth from about 5 microns to about 450 microns and a depth:width aspect ratio of at least 3:1;
  • barrier layer over the dielectric layer when present, or over the inner surface of the via, wherein the barrier layer is or comprises a material which inhibits diffusion of copper into the silicon substrate;
  • the silicon substrate into an electrolytic bath in an electrolytic copper plating system with the basic metal layer connected as a cathode, the system further comprising an insoluble dimensionally stable anode and a source of copper metal, wherein the electrolytic bath comprises an acid, a source of copper ions, a source of ferrous and/or ferric ions, and at least one additive for controlling physical-mechanical properties of deposited copper; and
  • the silicon substrate is provided with vias already formed.
  • the vias may be formed by any appropriate method, and are most often formed by reactive ion etching.
  • the inner surface of the via will be formed of the silicon of the silicon substrate or, it may be formed of a reaction product resulting from the reactive ion etching.
  • the inner surface of the via may contain or consist of a silicon halide, such as silicon hexafluoride.
  • the reactive ion etching has been carried out with oxygen present, the inner surface of the amount contain or consist of silicon dioxide.
  • the barrier layer is formed of a material, such as silicon nitride, which functions both as a barrier as described, and as a dielectric, in which case a separate dielectric layer need not be provided, and the step (2) above can be omitted.
  • the vias may be formed with a dielectric layer in place. For example, when a gas is present in the via formation step which, when reacted with silicon, forms a dielectric silicon compound, the via may be formed with the dielectric layer in place.
  • the step of applying is effective to electrodeposit the high purity copper to completely fill the via.
  • the step of applying an electrical voltage between the insoluble dimensionally stable anode and the basic metal layer, so that a current flows therebetween is carried out for a time sufficient to electrodeposit high purity copper to completely fill the via and to form a TSV having no inner cavity.
  • the step of applying is effective to electrodeposit the high purity copper to form a copper lining in the via of sufficient thickness to be capable of function as a TSV.
  • the step of applying an electrical voltage between the insoluble dimensionally stable anode and the basic metal layer, so that a current flows therebetween is carried out only for a time sufficient to electrodeposit high purity copper to line the via with a layer of high purity copper sufficient to provide the needed conductance.
  • a TSV is formed having an inner cavity of whatever size remains after the via has been electroplated with sufficient copper.
  • the deposited high purity copper is either substantially free of internal stress or includes a level of internal stress that does not result in bending of the silicon substrate upon subsequent processing.
  • the presence of internal stress in the deposited high purity copper can result in bending or deformation of the substrate upon heating during subsequent process steps.
  • the deposited copper is substantially free of voids and non-copper inclusions. It is very desirable that the deposited high purity copper be free of voids and non-copper inclusions. If voids are present, upon subsequent heating, the voids can cause deformation or, in some cases, can result in an explosive release of gas pressure. Both the deformation and the explosive release would result in an unsatisfactory situation. Any non-copper inclusions that might be present would result in a change in the conductivity of the copper, and would therefore interfere with the function of the TSV. For these reasons the high purity copper deposit should not include any substantial amount of non-copper inclusions.
  • the basic metal layer is formed over the barrier layer by one or more of an electroless plating process, a physical deposition process, a chemical vapor deposition process, or a plasma-enhanced chemical vapor deposition process.
  • the basic metal layer is applied to the surface of the via in order to provide a suitable conductive surface for the electrodeposition of the high purity copper.
  • the chemical vapor deposition process and the plasma enhanced chemical vapor deposition process may be more preferred than a physical deposition process such as sputtering or an electroless plating process.
  • both the physical deposition process and the electroless plating process are both suitable for use when properly applied, as will be understood.
  • the basic metal layer only needs to be thick enough to provide a conductive surface onto which the copper can be electrodeposited in the subsequent step. This thickness could be as low as a few nanometers, e.g., from about one to about 10 nm. However, in order to assure that a sufficient coverage has been obtained it may be desirable to apply a somewhat thicker layer of the basic metal.
  • the basic metal layer has a thickness in the range from about 0.01 micron to about 0.5 micron (about 10 nm to about 500 nm). In another embodiment, the basic metal layer has a thickness in the range from about 0.02 micron to about 0.25 micron, and in another embodiment the basic metal layer has a thickness in the range from about 0.05 micron to about 0.2 micron.
  • the basic metal layer comprises copper.
  • the basic metal layer comprises high purity copper, in which the copper as substantially the same purity as the later deposited copper used to fill the via.
  • the basic metal layer may comprise metals other than copper, on the condition that the metal provide sufficient coverage to the inner wall of the via and that it provide sufficient conductivity for the electrodeposited copper to adhere.
  • the metals other than copper may include gold, silver, platinum, palladium, aluminum, or any of the transition metals.
  • copper would be the most preferred metal for use in the basic metal layer.
  • a barrier layer is formed in the via.
  • the barrier layer is needed to prevent diffusion of the high purity copper of the TSV into the silicon of the substrate in which the TSV is located.
  • the barrier layer may be made of any material that provides a sufficient barrier to diffusion of copper into the substrate.
  • the barrier layer may be comprised of any appropriate materials that prevent diffusion of copper atoms into the substrate, or that enable the barrier layer as a whole to inhibit such diffusion.
  • the barrier layer may be comprised of one or more layers including materials, such as tantalum, tantalum nitride, titanium, titanium nitride and/or other suitable materials.
  • the barrier layer is or comprises a material which inhibits the diffusion of copper into the substrate in which the TSV is formed, or the barrier layer contains a material or sub-layer which inhibits such diffusion of copper.
  • the barrier layer comprises tantalum.
  • the barrier layer may be formed of a material such as silicon nitride or silicon carbide or a silicon carbide nitride.
  • the barrier layer may be formed by advanced well-established sputter deposition techniques or by atomic layer deposition (ALD), depending on the device and process requirements.
  • the dielectric layer is present and comprises silicon dioxide. In one embodiment, the dielectric layer is present and comprises silicon nitride. In this embodiment, the silicon nitride may provide dual duty, by forming both a barrier to copper migration and a dielectric layer to prevent current leakage. In such case, as noted, the barrier layer can function both as barrier and as dielectric to provide electrical insulation as well as a barrier to migration of the copper (or other metal used to fill the via).
  • the bath used for the copper deposition additionally contains at least one substance for increasing the electrical conductance of the bath, for example sulfuric acid, methane sulfonic acid, pyrophosphoric acid, fluoroboric acid or amidosulfuric acid.
  • at least one substance for increasing the electrical conductance of the bath for example sulfuric acid, methane sulfonic acid, pyrophosphoric acid, fluoroboric acid or amidosulfuric acid.
  • the acid is concentrated sulfuric acid at a bath concentration in the range from about 50 to about 350 g/l, or from about 180 g/l to about 280 g/l, or from about 100 g/l to about 250 g/l, or from about 50 g/l to about 90 g/l
  • the source of copper ions is copper sulfate pentahydrate (CuSO 4 .5 H 2 O) at a bath concentration in the range from about 20 g/l to about 250 g/l, or from about 80 g/l to about 140 g/l, or from about 180 g/l to about 220 g/l.
  • ferrous and/or ferric ions is ferrous sulfate heptahydrate and/or ferric sulfate nonahydrate at a bath concentration in the range from about 1 to about 120 g/l, or from about 1 g/l to about 20 g/l, and
  • the at least one additive comprises one or more of a polymeric oxygen-containing compound, an organic sulfur compound, a thiourea compound or a polymeric phenazonium compound.
  • the electroplating bath according to the invention contains at least one additive compound for controlling the physical-mechanical properties of the copper layers.
  • Suitable additive compounds are, for example, polymeric oxygen-containing compounds, organic sulfur compounds, thiourea compounds, polymeric phenazonium compounds and polymeric nitrogen compounds, and mixtures or combinations of any two or more of any of these additive compounds.
  • Suitable, exemplary, polymeric oxygen-containing compounds include one or more of the following:
  • the polymeric oxygen-containing compounds additive compounds may be contained in the electrodeposition bath at a concentration in the range from about 0.005 g/l to about 20 g/l, and in one embodiment, from about 0.01 g/l to about 5 g/l.
  • Suitable, exemplary sulfur compounds with suitable functional groups for providing water solubility include one or more of the following:
  • Suitable, exemplary thiourea-type compounds include one or more of the following:
  • Suitable, exemplary phenazonium compounds include one or more of the following:
  • Suitable, exemplary polymeric nitrogen-containing compounds include one or more of the following:
  • the thiourea-type compounds, polymeric phenazonium compounds and polymeric nitrogen containing compounds, as the additive compounds, may be used at a concentration in the range from about 0.0001 g/l to about 0.50 g/l, and in one embodiment, from about 0.0005 g/l to about 0.04 g/l.
  • Fe(II) and/or Fe(III) compounds are contained in the bath.
  • Suitable iron salts are both the iron(II)-sulfate-heptahydrate and iron(III)-sulfate-nonahydrate, from either or both of which the effective Fe 2+ /Fe 3+ (Fe(III)/Fe(III)) redox system is formed after a short operational time.
  • These salts are mainly suitable for aqueous, acidic copper baths.
  • Other water-soluble iron salts may also be used, for example iron perchlorate. Salts which contain no (hard) complex formers are advantageous.
  • Such complex formers may be biologically non-degradable or only may be degradable with some difficulty, thus such salts may create problems when disposing off-rinsing water (for example iron ammonium alum).
  • carboxylates of iron ions, such as acetate, propionate and benzoate, as well as the hexafluorosilicates are also advantageous.
  • Suitable systems employing the Fe 2+ /Fe 3+ redox system are disclosed, for example, in U.S. Pat. Nos.
  • the concentration of the iron ion substance(s) may be as follows.
  • the iron ions are added as iron(II)-sulfate (FeSO 4 .7H 2 O) at a concentration in the range from about 1 g/l to about 120 g/l, and in one embodiment from about 20 g/l to about 80 g/l.
  • the bath is prepared to initially contain from about 1 g/l to about 30 g/l ferrous ions (based on actual Fe content, added as, e.g., ferrous sulfate heptahydrate) and from about 1 g/l to about 30 g/l ferric ions, in one embodiment, from about 2 to about 10 g/l, and in another embodiment, from about 3 to about 5 g/l (based on actual Fe 3+ content, added as, e.g., ferric sulfate nonahydrate).
  • ferrous ions based on actual Fe content, added as, e.g., ferrous sulfate heptahydrate
  • ferric ions in one embodiment, from about 2 to about 10 g/l, and in another embodiment, from about 3 to about 5 g/l (based on actual Fe 3+ content, added as, e.g., ferric sulfate nonahydrate).
  • the bath is prepared to initially contain from about 2 g/l to about 20 g/l ferrous ions (based on actual Fe 2+ content, added as, e.g., ferrous sulfate heptahydrate) and from 4 g/l to about 20 g/l ferric ions (based on actual Fe 3+ content, added as, e.g., ferric sulfate nonahydrate).
  • the bath is prepared to initially contain from about 3 g/l to about 10 g/l ferrous ions (based on actual Fe 2+ content, added as, e.g., ferrous sulfate heptahydrate) and from 5 g/l to about 20 g/l ferric ions (based on actual Fe 3+ content, added as, e.g., ferric sulfate nonahydrate).
  • ferrous ions based on actual Fe 2+ content, added as, e.g., ferrous sulfate heptahydrate
  • ferric ions based on actual Fe 3+ content, added as, e.g., ferric sulfate nonahydrate.
  • copper ions consumed during the deposition from the deposition solution cannot be directly supplied by the anodes by dissolution when insoluble anodes are used, these copper ions are supplemented by chemically dissolving corresponding copper parts or copper-containing shaped bodies.
  • copper ions are formed from the copper parts or shaped bodies in a redox reaction by the oxidizing effect of the Fe(III) compounds contained in the deposition solution, in which the Fe(III) ions are reduced to Fe(II) ions by the copper metal being oxidized to form Cu(II) ions in the electroplating bath, as described above.
  • the total concentration of the copper ions contained in the deposition solution is kept relatively constant, and the anodes remain the same uniform size.
  • the deposition solution passes from the copper ion generator back again into the electrolyte chamber which is in contact with the wafers and the anodes. As will be recognized, the following reactions take place:
  • At the cathode e.g., at the semiconductor substrate:
  • the system may be initialized with either or both a source of ferrous ion or a source of ferric ion, since the redox reaction interconverts these ions as the process proceeds.
  • the system is initialized with both a source of ferrous ions and a source of ferric ions.
  • the electrodeposition bath is substantially free of an added chloride, for example sodium chloride or hydrochloric acid.
  • Chlorides have been used in similar electroplating baths, but in accordance with this embodiment of the present invention, the chloride is omitted.
  • a possible bath component is omitted from the bath, or when a bath is referred to as being “free of” a component, this means that none of the component is intentionally added to the bath. Small amounts of such components may be present as impurities, but they are not added intentionally.
  • a voltage is applied between the semiconductor substrate and the anode, the voltage being so selected that an electric current of 0.05 amps per dm 2 (A/dm 2 ) to 20 A/dm 2 , in one embodiment, 0.2 A/dm 2 to 10 A/dm 2 and, in another embodiment, 0.5 A/dm 2 to 5 A/dm 2 , where the current flows are expressed as amps per dm 2 of, e.g., semiconductor substrate surface, assuming that the plating is applied to the entire surface of the substrate.
  • a pulse current or pulse voltage method is used.
  • the current between the workpieces, polarized as the cathode, and the anodes is set galvanostatically and modulated per unit time by suitable means.
  • a voltage between the wafers, as cathodes, and the counter-electrodes, as anodes is set potentiostatically, and the voltage is modulated per unit time so that a current is set which is variable per unit time.
  • the method which is known as the reverse pulse method, in one embodiment is used with bipolar pulses.
  • the bipolar pulses comprise a sequence of cathodic pulses, lasting from 20 milliseconds to 100 milliseconds, and anodic pulses lasting from 0.3 milliseconds to 10 milliseconds.
  • the peak current of the anodic pulses is set to at least the same value as the peak current of the cathodic pulses. In one embodiment, the peak current of the anodic pulses is set two to three times as high as the peak current of the cathodic pulses.
  • the electrical voltage is applied in a pulse current or a pulse voltage. In one embodiment, the electrical voltage is applied in a reverse pulse form with bipolar pulses.
  • the electrical voltage is applied in a reverse pulse form with bipolar pulses including a forward current pulse and a reverse current pulse.
  • the duration of the reverse current pulse is adjusted to about 1 to about 20 milliseconds, and in another embodiment, the duration of the reverse current pulse is adjusted to about 2 to about 10 milliseconds.
  • the duration of the forward current pulse is adjusted to about 10 to about 200 milliseconds, and in another embodiment, the duration of the forward current pulse is adjusted to about 20 to about 100 milliseconds.
  • peak current density of the forward current pulse at a work piece surface is adjusted to a maximum of about 15 amps per square decimeter (A/dm 2 ), and in another embodiment, peak current density of the forward current pulse at a work piece surface is adjusted to a maximum of about 1.5 to about 8 A/dm 2 .
  • the peak current density of the reverse current pulse at a work piece surface is adjusted to a maximum of about 60 A/dm 2 , and in another embodiment, peak current density of the reverse current pulse at a work piece surface is adjusted to a maximum of about 30 to about 50 A/dm 2 .
  • a first current pulse is shifted with respect to a second current pulse by about 180°.
  • a pause of suitable duration may be included between the first current pulse and the second current pulse.
  • a suitable duration may range, for example, from about 1 millisecond to about 5 milliseconds, and in one embodiment is from about 2 milliseconds to about 4 milliseconds, and in one embodiment, is about 4 milliseconds.
  • the redox system according to the present invention when compared to a copper electrodeposition system in which the redox system of the present invention is not used or not present, exhibits reduced consumption of organic additives. This unexpected benefit is believed to result from reduced oxidation of the organic additives at the anodes. In one embodiment, when compared to a copper electrodeposition system in which the redox system is not used or present, the redox system according to the present invention consumes only about 30% of the organic additives that would be consumed by the non-redox system.
  • no soluble anodes made of copper are used as the anodes; rather, dimensionally stable, insoluble anodes are used.
  • a constant spacing can be set between the anodes and the wafers.
  • the anodes are easily adaptable to the wafers in respect of their geometrical shape and, contrary to soluble anodes, they substantially do not change their geometrical external dimensions. In consequence, the spacing between the anodes and the wafers, which can influence the distribution of layer thickness on the surface of the wafers, remains constant. Without such constant spacing, variations in layer thickness and quality may result, causing non-uniform copper deposits.
  • insoluble anodes materials which are resistant to the electrolyte are used, such as stainless steel or lead for example.
  • Anodes may be used which contain titanium or tantalum as the basic material, which may be coated with noble metals or oxides of the noble metals. Platinum, iridium or ruthenium, as well as the oxides or mixed oxides of these metals, may be used, for example, as the anode coating. Besides platinum, iridium and ruthenium, rhodium, palladium, osmium, silver and gold, or respectively the oxides and mixed oxides thereof, may also be used for the anode coating.
  • a particularly high resistance to the electrolysis conditions may be obtained, for example, on a titanium anode having an iridium oxide surface, which was irradiated with fine particles, spherical bodies for example, and thereby compressed in a pore-free manner.
  • anodes may be used which are formed from noble metals, for example platinum, gold or rhodium or alloys of these metals.
  • Other inert, electrically conductive materials, such as carbon (graphite), may also be used.
  • the wafers are processed in a horizontal orientation for the copper deposition.
  • Anodes in the deposition bath also kept horizontal, are disposed directly opposite the wafers. Since dimensionally stable insoluble electrodes are employed, the distance between the anodes and the cathodic parts of the wafer or semiconductor device is maintained substantially constant.
  • the process according to the invention is especially suitable for filling vias to form TSVs in silicon substrates in, e.g., semiconductor devices, silicon wafers and MEMS devices.
  • a dielectric layer is formed on the inner surface of the vias, during or subsequent to the step of etching to form the initial vias.
  • the oxidation of silicon results in the formation of silicon dioxide, and this dielectric material may be employed to provide electrical isolation of the TSVs from the surrounding silicon substrate, chip or wafer.
  • the dielectric layer may be formed by any suitable process.
  • a silicon dioxide layer is formed, for example, by a TEOS process or by an oxidation of the silicon sidewalls of the via. Suitable methods for formation of a layer of such dielectric materials are known in the art and may be selected by the person of skill in the art as needed.
  • a barrier layer is formed on the inner sidewalls of the TSV, in order to provide a barrier to diffusion of the later-deposited copper into the silicon of the substrate through which the TSV is formed.
  • the barrier layer is a tantalum-containing material capable of reducing and/or eliminating diffusion of copper therethrough.
  • a nitride layer (tantalum nitride layer for example) is formed, for example, by a sputtering process. Suitable methods for formation of a layer of such barrier materials are known in the art and may be selected by the person of skill in the art as needed.
  • the barrier layer may be made electrically conductive by deposition of a suitable base metal layer over the barrier layer.
  • the base metal layer is subsequently applied, which forms an electrically conductive base for the subsequent electrolytic metallization.
  • the base metal layer is applied by a physical metal deposition process and/or by a CVD process and/or by a PECVD process.
  • a plating process may also be used, for example an electroless metal deposition process.
  • a basic metal layer formed from copper may be deposited.
  • Other conductive layers, usually metal layers, may also be suitable.
  • Such conductive layers may include, for example, a metal such as tungsten, silver, gold, platinum, zinc, tin or any other metal or silicide known for use as a seed layer for electrodeposition of copper onto a non-conductive substrate.
  • the copper fill for the TSV is electrolytically deposited according to the above-described process.
  • the process of the present invention is integrated into a semiconductor fabrication process, and includes
  • barrier layer by physical vapor deposition, thermal and/or CVD,
  • the wafer or semiconductor device may then be processed using standard technology, such as CMOS, and later subjected to processes such as thinning, lithography, solder bump, dicing and then die-to-die, die-to-wafer, wafer-to-wafer or other appropriate 3D construction by various known methods.
  • CMOS complementary metal-oxide-semiconductor
  • manufacturing aspects relating to TSVs may include via formation, metallization, wafer thinning, alignment, and bonding.
  • a wafer is provided with vias having a diameter of about 10 microns and a depth of about 50 microns.
  • the vias are initially coated with a dielectric layer of silicon dioxide formed by high temperature oxidation of the inner sidewalls of the vias.
  • the dielectric layer on the inner sidewalls of the vias is next coated with a diffusion barrier layer formed from tantalum nitride applied by sputtering.
  • the diffusion barrier layer is coated with a copper base metal layer by a sputtering process, in which the copper base metal layer has a thickness of about 0.1 micron.
  • the wafer is then immersed in a copper deposition bath described below in which the wafer is connected as a cathode and an insoluble anode is included.
  • the via is filled with high purity copper by electrodeposition from the bath having the following ingredients, to form the TSVs in accordance with the present invention:
  • the high purity copper is electrodeposited under the following conditions:
  • Pulsed current is applied with the parameters shown in the table below.
  • the internal stress is measured as deposited without a post-annealing step.
  • the measurement is via wafer warpage and bow (LASER measurement).
  • the equipment used was a KLA-TENCOR FLX-2320 thin film stress measurement system, copper film thickness 1 micron, wafer thickness 750 micron.
  • FIG. 1 is a schematic cross-sectional view of a 3D device 100 including a substrate 102 having mounted thereon two wafers 104 and 106 , including copper-filled TSVs 108 a , 108 b , 108 c , 110 a , 110 b and 110 c , in which the TSVs have been electrodeposited by a process according to an embodiment of the present invention.
  • the substrate 102 may be any suitable substrate, such as a chip, a wafer or some other substrate upon which one or more chips or wafers is to be attached to form a 3D device such as the 3D device 100 depicted in FIG. 1 . As shown in FIG.
  • the 3D device 100 further includes solder bumps 112 a , 112 b , 112 c , 114 a , 114 b and 114 c , by which the respective filled TSVs 108 a , 108 b , 108 c , 110 a , 110 b and 110 c are electrically interconnected to each other and to electrical wiring 116 in the substrate 102 .
  • the 3D device 100 further includes under fill material 118 between the wafer 104 and the substrate 102 and between the wafer 104 and the wafer 106 . It is noted that FIG.
  • FIG. 1 is a highly schematic depiction of a 3D device, and for the sake of clarity and simple explanation omits the various functional elements that would be present in the various elements of the 3D device, so as to more clearly depict the important elements of the 3D device which can be formed by a process including various embodiments of the present invention.
  • FIGS. 2-9 are schematic cross-sectional views of steps in a process of forming TSVs in a wafer and mounting the wafer onto a substrate to form part of a 3D device such as the 3D device 100 shown in FIG. 1 , in accordance with an embodiment of the present invention.
  • the process depicted in FIGS. 2-9 is presented schematically and, as will be understood, may be carried out in the appropriate selected order as described above, with respect to the “via first” or “via last”, before or after FEOL and before or after bonding.
  • FIG. 2 depicts a silicon substrate, such as a wafer, chip or other silicon substrate which may be used, e.g., in a semiconductor device, through which TSVs are to be formed.
  • a silicon substrate such as a wafer, chip or other silicon substrate which may be used, e.g., in a semiconductor device, through which TSVs are to be formed.
  • TSVs are formed in the silicon substrate 104 .
  • any suitable method of forming TSVs may be used, and in one embodiment, the method is DRIE. This formation is indicated by the arrow leading from FIG. 2 to FIG. 3 .
  • FIG. 3 depicts the silicon substrate of FIG. 2 after the TSVs 120 a , 120 b and 120 c have been formed through most of the thickness of the silicon substrate 104 .
  • TSVs 120 a - 120 c are depicted in FIGS. 1-8 , but as disclosed above, a given wafer or semiconductor device may contain hundreds or thousands of such TSVs.
  • the TSVs 120 a - 120 c in FIG. 3 and in all of the FIGS. 1 and 3 - 9 , are shown as having vertical, parallel sidewalls; this is for purposes of ease of illustration and is not intended to depict a required situation.
  • the sidewalls in TSVs generally taper slightly from top to bottom, i.e., from the opening of the via to the bottom of the via, so that the diameter at the bottom is slightly smaller than the diameter at the top opening or mouth of the via.
  • a dielectric layer 122 on the entire inside surface of the sidewalls of each TSV 120 there optionally may be deposited a dielectric layer 122 , as shown in FIGS. 4 and 4 a . Due to the scale of FIG. 4 , an expanded view of a portion of the TSV 120 c and the subsequently applied layers are shown in FIGS. 4 a , 4 b and 4 c . As described above, the dielectric layer 122 is provided as an electrical insulation layer between the subsequently formed conductive fill of the TSV and the adjacent silicon substrate 104 .
  • each TSV 120 a - 120 c should be covered with the dielectric layer 122 .
  • the relative proportions of the layers and the substrate 104 are not to scale.
  • the dielectric layer is optional, and in an appropriate embodiment, the step illustrated in FIG. 4a can be omitted, e.g., when the barrier layer subsequently formed also functions as a dielectric.
  • a barrier layer 124 is deposited or formed over the dielectric layer 122 , as shown in FIG. 4 b .
  • the barrier layer may be formed of a material such as, for example, tantalum (Ta), tantalum/tungsten (TaW) or tantalum nitride (TaN), or other material known to function as a barrier to copper migration.
  • the barrier layer 124 is provided in order to prevent migration of copper into the adjacent silicon substrate 104 .
  • the barrier layer may be deposited by any appropriate method known in the art for deposition of such a layer.
  • a conductive base metal or seed layer 126 is deposited on the surface of the barrier layer 124 lining the TSVs 120 a - 120 c .
  • the base metal layer 126 may be any appropriate conductive metal layer, and in one embodiment is copper, and in another embodiment is high-purity copper.
  • the base metal layer 126 may be deposited by any appropriate method known in the art for deposition of such a layer.
  • the base metal layer 126 provides a conductive surface upon which the electrodeposition of the TSV fill metal can take place.
  • each of the TSVs 120 a - 120 c are filled with high purity copper by an electrodeposition process as described above, to form the filled TSVs 108 a - 108 c , as depicted in FIG. 5 .
  • the high purity copper is electrodeposited using the redox system described above, such that the copper is deposited on the base metal layer 126 , and the high purity copper completely fills the TSVs with essentially no voids or inclusions, in accordance with an embodiment of the present invention.
  • FIGS. 1 and 5 - 9 although the dielectric layer 122 , the barrier layer 124 and the conductive layer 126 are not clearly shown due to the scale of the drawings, they are deemed to be present, having been formed as described above, and shown in FIGS. 4 a , 4 b and 4 c.
  • FIGS. 6-9 schematically depict certain steps in a process of attaching a silicon substrate 104 containing the filled TSVs 108 a - 108 c to the substrate 102 .
  • any needed removal of the variously deposited layers from other surfaces of the wafer may be carried out.
  • the copper electrodeposition may cover the entire upper surface of the wafer, and may be removed, e.g., by chemical-mechanical polishing (CMP).
  • CMP chemical-mechanical polishing
  • Suitable methods for removing excess material deposited in the course of carrying out the processes described herein may be selected as needed by those of skill in the art.
  • the wafer containing the newly formed TSVs 108 a - 108 c has been thinned, thus exposing the lower or bottom end of the TSVs 108 a - 108 c to enable electrical connection of the TSVs 108 a - 108 c in subsequent steps.
  • the thinning may be carried out by any known method for thinning semiconductor wafers, chips, etc.
  • the silicon substrate 104 containing the filled TSVs 108 a - 108 c is positioned above or adjacent to the substrate 102 .
  • the substrate 102 includes the electrical wiring 116 , similar to that shown in FIG. 1 .
  • solder beads or balls 112 a , 112 b and 112 c have been placed in locations at which the TSVs 108 a - 108 c will contact exposed portions of the electrical wiring 116 .
  • the solder beads 112 a - 112 c may be formed of any suitable material, such as tin-lead solder or any other known solder material used for making such attachments, and may be deposited according to any known method.
  • the next step is contacting each of the TSVs 108 a - 108 c to the solder beads 112 a - 112 c , which are in turn in contact with the electrical wiring 116 in the substrate 102 , and thereby to create an electrical connection between the respective TSVs 108 a - 108 c to the electrical wiring 116 via the respective solder beads 112 a - 112 c .
  • the contacting may be by any known method.
  • the underfill material 118 a can be added to fill the or any space remaining between the silicon substrate 104 and the substrate 102 .
  • the underfill material is placed following the step of contacting the TSVs to the solder beads, and in another embodiment, the underfill material 118 a is applied to the substrate prior to the contacting. As will be understood, the underfill material 118 a may be applied before or after the solder beads.
  • the step of etching may form TSVs that penetrate through the entire thickness of the silicon substrate (not shown).
  • a lower layer to which the wafer has already been bonded may act as an etch stop layer.
  • the high conductivity of the copper may be sufficient to provide the electrical conductivity required of the TSVs.
  • FIGS. 10-12 are schematic cross-sectional views of steps in a process of forming TSVs in a wafer and mounting the wafer onto a substrate to form part of a 3D device in accordance with another embodiment of the present invention.
  • FIG. 10 depicts the wafer into which a TSV is being formed at a point in the process corresponding to FIG. 4 c , after the via 220 has been formed, a dielectric layer 222 , a barrier layer 224 and a base metal conductive layer 226 have been deposited on the sidewalls in sequence as described with the embodiment of FIGS. 4 , 4 a , 4 b and 4 c , and in which the materials deposited and methods therefore are the same as have been described above.
  • each of the vias 220 are lined, but are not completely filled, with a relatively thick and uniform layer of highly pure copper by an electrodeposition process as described above, to form the lined TSVs 208 , as depicted in FIG. 11 .
  • the highly pure copper is electrodeposited using the redox system described above, such that the copper is deposited on the base metal layer 226 , and the highly pure copper completely lines the inner walls of the TSVs with a thick layer of the highly pure copper.
  • the layer of high purity copper itself contains essentially no voids or inclusions, in accordance with an embodiment of the present invention.
  • the layer has a thickness which, when coupled with the relatively large size of the TSV, provides adequate conductivity without requiring the TSV 208 to be completely filled.
  • the TSV 208 includes one large, central opening 228 , in that the via 220 has not been completely filled but instead is covered with a uniformly thick layer of the high purity copper by the process in accordance with this embodiment of the invention.
  • the wafer 200 is then thinned to provide the wafer at the stage shown in FIG. 12 .
  • the wafer containing the newly formed TSVs 208 has been thinned, thus exposing the lower or bottom end of the TSVs 208 to enable electrical connection of the TSVs 208 in subsequent steps.
  • the thinning may be carried out by any known method for thinning semiconductor wafers, chips, etc.
  • the layers including the dielectric layer 222 , the barrier layer 224 , the base metal layer 226 and the high purity copper layer 208 have not yet been removed from the upper surface of the wafer 200 .
  • These layers would also be present in the embodiment of the invention described with respect to FIGS. 2-9 , but in describing that embodiment, the step of removing these layers was not specifically described. Such step would have been carried out subsequent to the step of electroplating with high purity copper in accordance with the invention, and had already been completed at the point in the process depicted in FIG. 5 .
  • FIG. 12 the layers including the dielectric layer 222 , the barrier layer 224 , the base metal layer 226 and the high purity copper layer 208 have not yet been removed from the upper surface of the wafer 200 .
  • These layers would also be present in the embodiment of the invention described with respect to FIGS. 2-9 , but in describing that embodiment, the step of removing these layers was not specifically described. Such step would have been carried out subsequent to the step of electroplating with high purity copper
  • the copper layer can simply be removed, e.g., by CMP, or it can be patterned to create an electrical circuit on that surface of the wafer.
  • the pattern may be formed by a photoresist process prior to the step of electroplating with high purity copper. While it is also possible to carry out the pattern formation steps subsequent to the step of electroplating with high purity copper, it is considered to be more efficient to form the pattern, e.g., by a photoresist process, prior to the step of electroplating with high purity copper.

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US12/372,113 2009-02-17 2009-02-17 Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv) Abandoned US20100206737A1 (en)

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US12/372,113 US20100206737A1 (en) 2009-02-17 2009-02-17 Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv)
CN200980156992.4A CN102318041B (zh) 2009-02-17 2009-12-16 用于电沉积铜的工艺，在穿硅通孔(tsv)中的芯片间、芯片到晶片间和晶片间的互连
PCT/IB2009/007793 WO2010094998A1 (en) 2009-02-17 2009-12-16 Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv)
EP09799392.7A EP2399281B1 (en) 2009-02-17 2009-12-16 Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv)
JP2011549685A JP5743907B2 (ja) 2009-02-17 2009-12-16 スルーシリコンビア（ｔｓｖ）内にチップ−チップ間、チップ−ウェハー間及びウェハー−ウェハー間の銅インターコネクトを電着するプロセス
TW098144125A TW201034120A (en) 2009-02-17 2009-12-22 Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (TSV)

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JP2012518084A (ja) 2012-08-09
TW201034120A (en) 2010-09-16
WO2010094998A1 (en) 2010-08-26
EP2399281B1 (en) 2016-04-20
JP5743907B2 (ja) 2015-07-01

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