CN1965110A - Method of barrier layer surface treatment to enable direct copper plating on barrier metal - Google Patents
Method of barrier layer surface treatment to enable direct copper plating on barrier metal Download PDFInfo
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- CN1965110A CN1965110A CN 200580019070 CN200580019070A CN1965110A CN 1965110 A CN1965110 A CN 1965110A CN 200580019070 CN200580019070 CN 200580019070 CN 200580019070 A CN200580019070 A CN 200580019070A CN 1965110 A CN1965110 A CN 1965110A
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- 239000010949 copper Substances 0.000 title claims abstract description 129
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 125
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000007747 plating Methods 0.000 title claims abstract description 26
- 230000004888 barrier function Effects 0.000 title abstract description 23
- 238000004381 surface treatment Methods 0.000 title abstract 2
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 238000000137 annealing Methods 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000356 contaminant Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 238000009713 electroplating Methods 0.000 claims description 81
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 71
- 229910052707 ruthenium Inorganic materials 0.000 claims description 71
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000002203 pretreatment Methods 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
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- 239000006210 lotion Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 5
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- 235000003140 Panax quinquefolius Nutrition 0.000 description 3
- 240000005373 Panax quinquefolius Species 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001614291 Anoplistes Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- -1 tungsten nitride Chemical class 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
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- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
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- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- HWEYZGSCHQNNEH-UHFFFAOYSA-N silicon tantalum Chemical compound [Si].[Ta] HWEYZGSCHQNNEH-UHFFFAOYSA-N 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses embodiments of a method of barrier layer surface treatment to enable direct copper plating without copper seed layer. In one embodiment, a method of plating copper on a substrate with a group VIII metal layer on top comprises pre-treating the substrate surface by removing a group VIII metal surface oxide layer and/or surface contaminants and plating copper on the pre-treated group VIII metal surface. Pre-treating the substrate can be accomplished by annealing the substrate in an environment with a hydrogen-containing gas environment and/or a non-reactive gas(es) to group VIII, by a cathodic treatment in an acid-containing bath, or by immersing the substrate in an acid-containing bath.
Description
Technical field
The method that can be on the barrier metal direct copper-plated barrier layer surface of embodiments of the invention relate generally to is handled.
Background technology
/ 4th microns of Asias, multiple-layer metallization are one of gordian techniquies that is used for follow-on ultra-large integrated (VLSI) and great scale integrated (ULSI) semiconducter device.The multilayer interconnection that is in this technological core need be filled contact, via hole, circuit and is formed on other features that have in the large ratio of height to width hole.The reliable formation of these features is very important for the success of VLSI and ULSI and for the ongoing effort of current densities on improving single substrate and tube core and quality.
Increase along with current densities, the width of contact, via hole, circuit, further feature and intervenient dielectric substance can be decreased to less than 65nm, and dielectric layer thickness keeps substantially constant, result to make the depth-width ratio (that is, height is divided by width) of feature increase.Many traditional depositing treatment can't as one man be filled depth-width ratio and be surpassed 6: 1, particularly the semiconductor structure when depth-width ratio surpasses 10: 1.Therefore, the ratio that has feature height and a characteristic width at formation is the structure of the nothing cavity nano-scale of 6: 1 or bigger depth-width ratio, still has a large amount of work.
In addition, along with characteristic width reduces, device current keeps constant usually or increases, and causes the current density for the increase of these features.Element aluminum and aluminium alloy have been the conventional metals that is used to form via hole and circuit in the semiconducter device, this be because aluminium has observable low-resistivity, for good tackiness of most dielectric substance tool and patterning easily, and obtain highly purified aluminium easily.But aluminium has than the higher resistivity of other conducting metal such as copper.Aluminium also is subjected to the influence of electronic migration, causes the formation in cavity in the conductor.
Copper has the resistivity lower than aluminium with copper alloy, and compares with aluminium and to have obviously higher electronic migration impedance.For the higher current density that experiences under the device speed situation that is supported in highly integrated and increase, these characteristics are very important.Copper also has good thermal conductivity.Therefore copper becomes the selection metal of 1/4th microns of Asias, large ratio of height to width interconnect feature on the filling semiconductor substrate.
Traditionally, the deposition technique such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) has been used to fill these interconnect features.But,, use the interconnect feature in the no cavity that CVD and/or PVD undertake by the conventional metals technology to fill and become more and more difficult along with interconnect dimensions reduces and the increase of depth-width ratio.As a result, electroplating technology, for example electrochemistry plating (ECP) has become the feasible processing that is used for the large ratio of height to width interconnect feature of inferior 1/4th micron-scales of filling in the unicircuit manufacturing processing.
ECP handles the processing that needs two stages mostly, wherein at first on the surface of the feature on the substrate, form kind of a crystal layer (this processing can realize) in separate payment, surface with feature is exposed in the electrolyte solution then, applies electric electrical bias simultaneously between substrate surface and the anode in electrolyte solution.
Traditional plating practice comprises by physical vapor deposition (PVD), chemical vapor deposition (CVD) or ald (ALD) copper kind crystal layer is deposited on the diffusion impervious layer (for example tantalum or tantalum nitride).But, along with characteristic dimension becomes littler, because often obtain the island of discontinuous copper caking, so utilize the PVD technology to be difficult to have the brilliant stage covering of suitable kind in the feature side-wall kind of close feature bottom.When using CVD or ALD depositing treatment to replace PVD to come on the entire depth of large ratio of height to width feature, to deposit the successive side wall layer, on this zone, form thick copper layer.Can cause inlet portion sealing before sidewall is covered fully of feature at the thick copper layer on this zone.When the deposit thickness on this zone is reduced preventing when sealing inlet, it is discontinuous that ALD and CVD technology also are easy in kind of crystal layer generation.Plant these the discontinuous defectives that cause in the layer that is plated on kind of the crystal layer that shown as in the crystal layer.In addition, copper is easy to quick oxidation in atmosphere, and cupric oxide can be dissolved in the electroplate liquid apace.For preventing the dissolving fully of the copper in the feature, copper kind crystal layer can be made usually thicker relatively (thick 800 that reach), and it can suppress electroplating processes feature is filled.Therefore, desired is in the copper electroplating processes that allows under the situation that does not have copper kind crystal layer directly copper to be electroplated on one or more thin barrier layers.
Therefore, there is the demand that need not the copper electroplating processes of copper kind crystal layer to feature can be filled.
Summary of the invention
The method that embodiments of the invention usually provide barrier layer surface to handle, it can directly copper plating under the situation that does not have copper kind crystal layer.In one embodiment, a kind of on substrate the method for Direct Electroplating copper, described substrate has the VIII family metal level on substrate surface, said method comprising the steps of: the described substrate surface of pre-treatment is to remove VIII family oxidation on metal surface thing layer and/or the organic surface contaminant on the described substrate surface, the critical current density during reducing to electroplate; Be plated on the described pretreated substrate surface with the copper layer of will be continuously in the acid electroplating body lotion with the electroplating current that is equal to or greater than described critical current density and not having a cavity.
Description of drawings
Read in conjunction with the drawings following detailed description, will readily appreciate that instruction of the present invention, in the accompanying drawing:
Figure 1A-1C illustrates the schematic cross sectional views that unicircuit is made sequence.
Fig. 2 shows the critical current density as the function of sulfuric acid concentration.
Fig. 3 A shows the schema on pre-processed substrate surface before copper is electroplated.
Fig. 3 B shows for deposition and annealed ruthenium substrate, as the critical current density of the function of sulfuric acid concentration.
Fig. 4 shows in 0.14 μ m * 0.8 μ m groove the SEM of galvanized copper on the ruthenium surface after the annealing.
Fig. 5 is the vertical view of an embodiment of electrochemistry electroplating system.
Fig. 6 illustrates the exemplary embodiment of the electroplating unit that uses in electrochemistry electroplating unit of the present invention.
For helping to understand, under possible situation, use same numeral to represent for accompanying drawing common similar elements.The accompanying drawing not drawn on scale.
Embodiment
By CVD, ALD or the sedimentary ruthenium of PVD (Ru) film can be for the potential candidate that nothing between inter-metal dielectric (IMD) and the copper-connection is planted brilliant diffusion barrier that is used for less than the 45nm technology.Ruthenium is a VIII family metal, has low-resistivity (resistivity～7 μ W-cm) and high thermal stability (high-melting-point～2300 ℃).Ruthenium even exist under the situation of oxygen and water relatively stable at ambient temperature.The thermal conductivity of ruthenium and specific conductivity are the twices of tantalum (Ta).Ruthenium is not forming alloy with copper below 900 ℃, and has showed good adhesivity for copper.Therefore, semi-conductor industry is for ruthenium has been produced interest as copper barrier layer.When attempting to fill the feature that ruthenium applies with the state that do not have kind of crystal layer with copper, the low-resistivity of ruthenium is an advantage.
Figure 1A-1C illustrates the sectional view of the substrate that is combined with VIII family of the present invention different steps metal barrier, that be in copper-connection manufacturing sequence.For example, Figure 1A illustrates the sectional view of the substrate 100 with metal contact 104 and dielectric layer 102 formed thereon.Substrate 100 can comprise semiconductor material, as silicon, germanium or gallium arsenide.Dielectric layer 102 can comprise insulating material, and (SiOxCy, for example the registered trademark that can obtain from the Applied Materials that is positioned at California Sheng Take Laura is BLACKDIAMOND as silicon-dioxide, silicon nitride, silicon oxynitride and/or carbon doped silicon oxide
TMLow K dielectrics).Metal contact 104 can comprise for example copper or other material.Hole 120 can be defined in the dielectric layer 102, so that the opening on the metal contact 104 to be provided.Can use conventional lithography or etching technique in dielectric layer 102, to define hole 120.The width of hole 120 can be equal to or less than about 900 .The thickness of dielectric layer 102 can be at about 1000 to the scope between about 10000 .
In one embodiment, blocking layer 106 can be formed in the hole 120 that defines in the dielectric layer 102.Optical barrier layer 106 can comprise one or more layers that contain refractory metal, as copper blocking material, for example titanium, titanium nitride, titanium silicon nitride, tantalum, tantalum nitride, tantalum silicon nitride, tungsten, tungsten nitride and other material.Can use the suitable depositing treatment such as ALD, chemical vapor deposition (CVD) or physical vapor deposition (PVD) to form optical barrier layer 106.For example, the CVD that can use wherein titanium tetrachloride and ammonia to react handles or ALD handles depositing titanium nitride.In one embodiment, the described ALD processing of U.S. Patent Publication 20030121608 (it is incorporated into this by reference) by as disclosed common transfer on the 3rd July in 2003 comes deposition of tantalum and/or tantalum nitride as the blocking layer.Optionally the thickness on blocking layer, and is preferably less than 100 between about 150 at about 5 .
In one embodiment, for example for ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), can be used as the bottom (or blocking layer) of copper via hole or circuit with the film of the VIII family metal of platinum (Pt).These VIII family metals that can resist corrosion and oxidation can provide following surface, and utilizing electrochemistry plating (ECP) to handle can deposit the copper layer thereon subsequently.VIII family metal is used for copper barrier layer.VIII family metal can also be deposited on traditional blocking layer (for example Ta (tantalum) and/or TaN (tantalum nitride)), to serve as the bonding coat between conventional barrier and the copper.Usually use chemical vapor deposition (CVD) processing, ald (ALD) processing or physical vapor deposition (PVD) to handle and deposit VIII family metal.
With reference to Figure 1B, VIII family barrier metal layer 108 (for example ruthenium) is formed on the substrate, and is formed in this example on the optional blocking layer 106.The thickness of VIII family metal level 108 depends on device architecture to be made usually.Usually, the thickness of VIII family metal level 108 (for example ruthenium) is less than about 1000 , preferably at about 5 between about 200 .In one embodiment, VIII family metal level 108 is to have the ruthenium layer of thickness less than about 100 (for example about 50 ).
Thereafter with reference to figure 1C, hole 120 can be filled by copper 110, to realize copper-connection.In one embodiment, precious metal or transition metal layer (for example ruthenium layer) can be used as kind of a crystal layer, and copper utilizes ECP plating or other copper electroplating technology directly to deposit to this kind crystal layer.The electrochemistry plating liquor that is used for ECP generally includes copper source, acid source, chloride-ion source and at least a electroplating solution additive (being level agent, inhibitor, promotor, antifoam agent etc.).For example, electroplating solution can comprise the copper between about 30g/l and the about 60g/l, about 10g/l to the interpolation level agent between interpolation inhibitor, about 1ml/l and the about 6ml/l between interpolation promotor, about 100ppm and the about 1000ppm between chlorion, about 5ppm and the about 30ppm between sulfuric acid, about 20ppm and the about 100ppm of about 50g/L.Electroplating current can be from 2mA/cm
2To 10mA/cm
2Scope in, be used for copper is filled into sub-micron trenches and via structure.The example of agent of copper electroplating chemical and processing can be submitted on July 8th, 2003, the Application No. 10/616 that is entitled as the common transfer of " Multiple-Step Electrodeposition Process For Direct CopperPlating On Barrier Metals ", 097, with on October 10th, 2003 submitted, be entitled as in the Application No. 60/510,190 of " Methods And Chemistry For ProvidingInitial Conformal Electrochemical Deposition Of Copper In Sub-MicroFeatures " and find.The example and the exemplary plating unit of electrochemistry plating (ECP) system below will be described in Fig. 5-6.
Have been found that the H that uses 10-50g/l
2SO
4And 2-10mA/cm
2The traditional copper electroplating processes of electroplating current density can not produce successive copper film (≤1000 ) deposition on the ruthenium layer.As electroplating current density and/or H
2SO
4Concentration (or acidity) increases to traditional copper and electroplates employed value when above, forms the successive copper film on the ruthenium layer.Minimum or critical current density (CCD) have been found when electroplating current density is equal to or greater than this value, will form successive copper film on the ruthenium layer, and when electroplating current density is worth less than this, will can not form successive copper film on the ruthenium layer.The size of CCD has greatly relevant with the acidity of electroplating solution.
Fig. 2 illustrates critical current density (CCD) and sulfuric acid (H
2SO
4) relation of concentration.As shown in Figure 2, CCD is defined in and forms the required minimum electrical current density of the continuous copper film of 1000 on the ruthenium surface.Value below CCD will can not deposit visually slick continuous copper film in the central area of substrate.Though the size of CCD and the acidity of plating bath have greatly relevant, CCD and ruthenium deposition method (no matter being ALD, CVD or PVD) are also uncorrelated.
As everyone knows, for the kinetics of the nucleation of galvanic deposit and crystalline growth with nucleation/growth position place when geo-electrochemistry overvoltage (over-potential) closely related.Overvoltage is defined as poor between actual potential and zero current (open circuit) current potential.Higher overvoltage is facilitated new crystallization nucleation by reducing critical nucleus size and increasing grain density; And lower electrochemistry overvoltage is facilitated the growth on existing crystallite.In addition, the sulfur-bearing organic additive in the electroplating solution (for example, promotor) is considered to strengthen the surface diffusion of the adatom (Cu adatoms) of copper, and promotes crystalline growth under the situation that consumes nucleation.The adatom of copper is meant during electroplating or before it is attached in the copper layer and lands in the copper atom of substrate surface.Because electroplating current density depends on the electrochemistry overvoltage that is used for given plating bath, so the sedimentary structure/form of copper is subjected to the influence of electroplating current density.(this copper film is at 3mA/cm having copper film
2The situation of electroplating current under in containing 10g/l vitriolic electroplating solution, electroplate 1000 (by measuring) copper film on the ruthenium film of 100 near edges of substrate) the center of substrate near in scanning type electron microscope (SEM) image got, find in the central zone of substrate, to have bigger crystal grain and relatively poor film deposits.The ruthenium film that 100 are thick deposits by PVD.According to result as shown in Figure 2, when sulfuric acid concentration was 10g/l, CCD was about 40mA/cm
23mA/cm
2Current density far below 40mA/cm
2(CCD), so according to expectation ground forms discontinuous layer.Thought that under this plating condition only the crystallite of minority is what enough to stablize to come as the nucleation centre of further crystalline growth, therefore the energy from electroplating current is mainly used in these crystallizations of growth, and helps the accelerated surface diffusion of the adatom of copper.Therefore SEM demonstrates crystal grain big in the substrate center zone and copper island deposition.Be to form the successive copper film on the entire substrate surface with this understanding, settled layer is had to very thick, and this settled layer will comprise the cavity easily, and this makes it be unsuitable for the application of copper-connection.Have been found that and use the H that contains 60g/l
2SO
4Electroplating solution and about 10mA/cm
2Electroplating current density (a little less than 15mA/cm
2CCD), can be formed on the substrate that has the thick continuous copper film of 5000 on the ruthenium film (it is that 100 are thick, and by PVD deposition).Yet there is big cavity at the interface at copper/ruthenium.
When electroplating current increases to 30mA/cm
2, find that grain density increases near the center of substrate, and find that grain-size reduces.But because electroplating current is lower than CCD, so on the ruthenium surface, form discontinuous copper film.As previously described, the ruthenium film is that 100 are thick and deposit by PVD.
Increase electroplating current and also have some shortcomings.Usually, high electroplating current density tends to cause relatively poor gap to fill.Usually, have been found that less than about 10mA/cm
2Electroplating current density can promote the gap that makes progress from the bottom to fill.For electroplating current density being reduced to the scope that fill in the gap that makes progress from the bottom that is suitable for, need to increase vitriolic concentration.When sulfuric acid concentration increases to 160g/l and electroplating current is 5mA/cm
2When (it is equal to the CCD under this specific acid concentration), on 100 ruthenium films on the substrate, form successive 1000 copper films.But section SEM pictorial display forms the cavity at the interface at copper/ruthenium.When electroplating current increases to 10mA/cm
2(5mA/cm
2The twice of CCD) and sulfuric acid concentration maintain 160g/l, successive 5000 copper films are formed on the ruthenium film of 100 and at copper/ruthenium does not have the cavity at the interface.
It is discussed above when the geo-electrochemistry overvoltage that CCD depends on that one of reason of body lotion acidity relates to.Electroplating solution with relatively low acidity has higher resistance.Therefore need high CCD to overcome the more high resistance that hangs down in the acidity plating bath.
23 to 27 March in 2003 in American Chemical Society's international conference that hold the New Orleans, Louisiana, the current research that people such as the Chyan of University of North Texas deliver shows, ruthenium oxide (RuO2) has the electroconductibility of metalloid, and copper also can be electroplated and be adhered on the ruthenium oxide securely.The result that viewed high CCD may be the existence of ruthenium surface oxidation and/or organic surface contaminant on the ruthenium deposition surface.Guess that the ruthenium surface of " pure " has more activity to the copper nucleation.Remove oxide layer or organic surface contaminant by the pretreatment technology before before copper is electroplated, can significantly reduce to forming continuous copper film does not have required electroplating current of copper/ruthenium interfacial voids and plating bath acidity.Pretreatment technology can be exposed to reductive agent with substrate surface.Fig. 3 A shows the pretreatment technology flow process.In step 301, the top has the substrate of VIII family metal (for example ruthenium) by the process quilt pre-treatment such as annealing and so in reducing gas (for example, hydrogen), with the metal oxide or the organic pollutant of clean surface.In step 302, the copper film Direct Electroplating is arrived pretreated substrate.Shown in the following equation (1) of a kind of possible redox reaction.
RuO
2+2H
2-----→Ru+2H
2O (1)
Come pre-treatment to have the substrate of 100 PVD ruthenium films by the annealing before and then copper is electroplated.This anneal have hydrogen-containing gas (synthesis gas that for example, contains 4% hydrogen and 96% nitrogen), room temperature to about 400 ℃ between (and preferably between about 100 ℃ to about 400 ℃) temperature, about 1sccm (standard cubic centimeter per minute) to the specific gas flow rate between about 20slm (standard Liter Per Minute) and about 5mTorr extremely under about 1500Torr lasting about 2 seconds extremely about 5 hours condition implement.For the consideration of making efficient, annealing time was preferably in 1 hour.The purpose of substrate annealing is for RuO
2Surface reduction is ruthenium and/or organic surface contaminant is separated out.In one embodiment, hydrogen-containing gas and non-reactive gas (for example, N
2Or rare gas element (for example, Ar, He etc.) mixes.For the purpose that organic surface contaminant is separated out, can use nonreactive gas for ruthenium (N for example
2Or rare gas element (as Ar)) anneals.Anneal can be carried out the single-chip rapid thermal annealing chamber that can obtain from the Applied Materials of California Sheng Take Laura, perhaps carries out in batch furnace.
Fig. 3 B illustrate the ruthenium deposition substrate in the annealing chamber shown in the bottom of Fig. 5 with 270 ℃ of examples of CCD situation about reducing after the annealing 30 seconds in synthesis gas.Curve 311 shows the copper-plated CCD that powers on ruthenium deposition substrate surface.Curve 312 shows at the synthesis gas annealed ruthenium substrate surface copper-plated CCD that reduces that powers on.For example for containing 10g/l vitriolic solution, CCD is from 40mA/cm
2Be reduced to 8mA/cm
2, for containing 100g/l vitriolic solution, CCD is from 10mA/cm
2Be reduced to 3mA/cm
2Curve 311 and 312 both all show CCD and reduce with the increase of acid concentration.The acid of using in the electroplating solution can be the acid of other types, for example sulfonic acid (comprising alkane sulfonic acid).If use another kind of acid substitution sulfuric acid, should use the angelic acid concentration range.
Under synthesis gas annealed situation, directly the copper electroplating processes can be operated with the current density similar to traditional copper electroplating processes.After synthesis gas annealing, the ruthenium substrate surface is tending towards becoming and has more wetting ability, as desired for cleaning and pure ruthenium surface.In order to keep significantly reducing of CCD, the copper on the synthesis gas annealing ruthenium film is electroplated and must be carried out in 4 hours after synthesis gas annealing, preferably carries out in 2 hours.If substrate is exposed to oxygen or other pollutent is too of a specified duration, then because RuO
xForm once more or from the deposition once more of organic surface contaminant of atmospheric environment, CCD will get back to the state before the annealing gradually.
Significantly reducing of the CCD that causes by hydrogen-containing gas annealing is extremely important because CCD reduce to allow to use comprise scope at about 10g/l acid CuSO of the actual acid concentration in about 300g/l scope extremely
4Body lotion, the current density of filling with the gap that is suitable for sub-micron trenches/via structure are come depositing copper film.
In one example, the 100g/l sulfuric acid concentration of electroplating solution and 3mA/cm contain to(for) use
2Electroplating current density (PCD) (equal CCD, PCD/CCD=1) sedimentary 1000 copper films on annealed 80 ALD rutheniums have deposited the successive copper film to its SEM pictorial display of getting, and do not have the cavity between copper/ruthenium interface.On copper/ruthenium interface, there are not good copper (Cu) of cavity expression and ruthenium interface integrity and copper in the lip-deep good adhesion of annealing ruthenium.In second example, contain the electroplating solution and the 4.5mA/cm of 100g/l sulfuric acid concentration for use
2Electroplating current density (or PCD/CCD=1.5) sedimentary 1000 copper films on annealed 80 ALD rutheniums, its SEM image of getting also shown deposited successive copper layer, and between copper/ruthenium interface, do not have the cavity.Similarly, 7.5mA/cm
2Electroplating current density (or PCD/CCD=2.5) also realized the successive copper film, and between copper/ruthenium interface, do not have the cavity.These results represent that the gas annealing pre-treatment reduces electroplating current density, and have improved the adhesion and the integrity at Ru/Cu interface.
When copper was deposited on synthesis gas annealed ruthenium surface, even when PCD/CCD equals 1, the Ru/Cu interface also showed the good integrity of not having the cavity.On the contrary, when electroplating with CCD (or PCD/CCD=1), the interface between copper and unannealed ruthenium surface will produce foregoing interfacial voids.The ruthenium surface of cleaning allows preferable copper nucleation and deposition, and has therefore improved the interface integrity.
Utilizing hydrogen-containing gas to anneal another advantage of pre-treatment VIII family metallic surface is the adhesion that improves between copper and the VIII family metal.Experimental result shows because good copper/ruthenium interface integrity (not having the cavity), and the adhesion between the ruthenium surface of copper and pretreated, cleaning and possibility non-oxidation is better.Good interface integrity between copper and the ruthenium layer is very important aspect for forming reliable semiconducter device.Obviously, pretreated ruthenium surface is crucial for form high-quality copper on the ruthenium film.
Copper is electroplated onto being on the other hand of synthesis gas annealed ruthenium surface, owing to having improved the covering of electroplating copper film that wetting ability causes as mentioned above to the entire substrate surface.The galvanized ladder of copper on the substrate feature covers and also can improve, because annealing ruthenium surface has more wetting ability, and more electroplating solution deeply can be caused in the feature.Fig. 4 shows in the groove of 0.14 μ m * 0.8 μ m the SEM that the copper-plated excellent clearance that powers on annealing ruthenium surface is filled.Sedimentary ruthenium is 80 ALD rutheniums.Pre-treatment is the synthesis gas annealing that continues 3 minutes at 300 ℃.The copper electroplating current is 10mA/cm when 100 initial
2, be 5mA/cm during all the other 1900
2
Anneal can or be carried out in isolating annealing system in the annealing chamber (annealing chamber 535 as shown in Figure 5) of one.Anneal can be carried out in single wafer chamber or batch furnace.
Except utilizing hydrogen-containing gas annealing, before Direct Electroplating copper, also can finish by additive method to the pre-treatment of VIII family metallic surface.An example of other pretreatment processs is the cathode treatment in the acid solution of no cupric ion.Surface RuO
xLayer can be by cathodic reduction, and organic surface contaminant that weak bond closes can be discharged from the surface by cathodic polarization.Following equation (2) shows a kind of possible reduction reaction.Cathode treatment can carried out in reference to the similar body unit of figure 6 described copper electroplating units with following, perhaps with the isolating processing unit of copper electroplating system in carry out.The cathode treatment unit needs anode, negative electrode and does not have the acid bath liquid of cupric ion.The acid concentration scope should be in the scope of about 10g/l between about 100g/l, and preferably at about 10g/l extremely in the scope between about 50g/l.Preferred acid is H
2SO
4, but also can use the acidic solution of other type, such as organic sulfonic acid solution (for example methylsulphonic acid).Acid bath need not have copper to avoid the deposition of the copper on ruthenium during the cathode treatment, and this copper deposition poorly makes copper island nucleation.
RuO
2+4H
*+4e
------>Ru+2H
2O (2)
Cathode treatment can realize by control of Electric potentials or current control.For the control of Electric potentials scheme, except that working electrode, need reference electrode to come the monitor wafer current potential, described working electrode is thin deposit ruthenium layer and the anode on wafer surface.Preferred reference electrode is the thin copper cash of arranging near substrate surface.Control of Electric potentials can realize by potentiostat.With respect to the copper reference potential, controlled ruthenium electrode current potential is in about 0 volt to about-0.5 volt scope.Except with RuO
xBe reduced to outside the Ru, H can take place on ruthenium film surface
2Develop.For current control scheme, cathodic current passes through between the substrate of deposit ruthenium and anode.Current density should be at about 0.05mA/cm
2To about 1mA/cm
2Scope in.Treatment time should be at about 2 seconds to about 30 minutes scope.But, consider that for output the treatment time preferably remained on below 5 minutes.
Experimental result relevant with ruthenium and discussion are only as example.Design of the present invention can be applied to other VIII family metals, for example rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt).
Copper is electroplated and can be carried out in the unit on Electra Cu ECP system or the SlimCell copper electroplating system, and both all can be obtained by the Applied Materials of California Sheng Take Laura.Fig. 5 illustrates the vertical view of SlimCell copper electroplating system 500.ECP system 500 comprises factor interface (FI) 530, and it generally also is called the substrate loading stage.Factor interface 530 comprises a plurality of substrate loading stages, and it is configured to engage with substrate accommodation box 534.Mechanical manipulator 532 is arranged in factor interface 530, and is configured to visit the substrate that is contained in the box 534.In addition, mechanical manipulator 532 also extends in the connecting passage 515, and connecting passage 515 is connected to factor interface 530 and handles main frame or platform 513.The position of mechanical manipulator 532 allows mechanical manipulator visit cassette of substrates 534 taking out substrate from it, and substrate is delivered to of the processing unit 514,516 that is arranged on the main frame 513, or is delivered to anneal station 535 alternatively.Similarly, after the substrate processing sequence was finished, mechanical manipulator 532 can be used for taking out substrate from processing unit 514,516 or anneal station 535.Under this situation, mechanical manipulator 532 can be sent substrate and get back to box 534 to remove from system 500.
To generally comprise two-position annealing chamber in the following anneal station that is described in more detail 535, wherein coolship/position 536 is adjacent to the location with heating plate/position 537, and has near the substrate transfer robot 540 (for example between two platforms) that is positioned at it.Mechanical manipulator 540 is configured to mobile substrate between each heating plate 537 and coolship 536 usually.In addition, though being depicted as to orientate as, annealing chamber 535 makes and to visit annealing chamber 535 from connecting passage 515 that embodiments of the invention are not limited to any specific structure or layout.In one embodiment, anneal station 535 can be orientated as with main frame 513 and directly be communicated with, that is, and and can be by 520 visits of main frame mechanical manipulator.For example, as shown in Figure 5, anneal station 535 is orientated as with the connecting passage 515 that allows to visit main frame 513 and directly is communicated with, and therefore, annealing chamber 535 is illustrated as with main frame 513 and is communicated with.The details of suitable annealing chamber has been described in the Application No. of submitting on April 18th, 2,003 60/463,860 that is entitled as " Two Position Anneal Chamber ".
In one embodiment, in the annealing chamber of one, carry out anneal, annealing chamber 535 as shown in Figure 5.In another embodiment, in isolating annealing system, carry out anneal.In other embodiments, in single wafer chamber or batch furnace, carry out anneal.
As mentioned above, ECP system 500 also comprises processing main frame 513, has the substrate transfer robot 520 that is positioned at the center on it.Mechanical manipulator 520 generally includes one or more arm/supporting plates 522,524, and it is configured to support and transmit substrate thereon.In addition, that mechanical manipulator 520 and appended supporting plate 522,524 are configured to usually is extensible, rotation and vertical shifting, makes mechanical manipulator 520 substrate can be inserted and shift out a plurality of processing position 502,504,506,508,510,512,514,516 that is positioned on the main frame 513.Similarly, factory interface robot 532 also comprises the ability of its substrate support supporting plate of extension, rotation and vertical shifting, also allows simultaneously to advance linearly along the mechanical manipulator track that extends to main frame 513 from factor interface 530.Usually, handling position 502,504,506,508,510,512,514,516 can be any amount of processing unit that utilizes in electrochemistry plating platform.More specifically, handle the position and can be configured to electrochemistry plating unit, cleaning unit, bevel clean unit, rotation cleaning-drying unit, substrate surface cleaning unit (its integral body comprises cleaning, cleans and the etching unit), electroless plating unit, Measuring and testing platform and/or other any processing unit that can advantageously be used in combination with the plating platform.In each processing unit and the mechanical manipulator each communicated by letter with processing controller 511 usually, processing controller 511 can be based on the Controlling System of microprocessor, it is configured to receive input from user and/or the various transmitters that are positioned in the system 500, and comes the suitably operation of Controlling System 500 according to input.
Fig. 6 illustrates the part sectional block diagram of the electroplating chamber 600 on the processing position 502,504,506,508,510,512,514,516 that can be embodied in Fig. 5.Electrochemistry plating unit 600 generally includes outer basin 601 and the interior basin 602 that is positioned in the outer basin 601.Interior basin 602 is configured to comprise electroplating solution usually, and it is used for during the electrochemistry plating is handled for example metal of copper and so on being plated to substrate.During electroplating processes, basin 602 (for example in electroplating solution was fed to usually continuously, for 10 liters electroplating units is about 1 gallon of per minute), and therefore in making electroplating solution overflow being crossed continuously basin 602 go up point (so-called " weir ") most, and by outer basin 601 collections and from its discharge, to be used for chemical treatment and recirculation.Usually with inclination angle location, that is, the frame part 603 of electroplating unit 600 raises on a side electroplating unit 600 usually, makes the parts of electroplating unit 600 tilt between about 3 ° and about 30 °, or for optimum result usually between about 4 ° and about 10 °.The framing member 603 support levels annular matrix member at an upper portion thereof of electroplating unit 600.Because framing member 603 raises on a side, so the upper surface of base member 604 tilts with certain angle with respect to horizontal tilt usually, this angle is corresponding to the angle of framing member 603 with respect to level attitude.Base member 604 comprises the formation annular or the disc shaped recesses of part in the central, and annular recess is configured to take in disc anode member 605.Base member 604 also comprises a plurality of fluid intakes/outlet 609 of extending from its lower surface.In fluid intake/outlet 609 each is constructed to the anodal compartment of electroplating unit 600 or cathodic compartment are supplied or exhaust fluid individually usually.Anode member 605 generally includes a plurality of grooves 607 that form by it, and wherein groove 607 is positioned in orientation parallel to each other on the surface of anode assemblies 605 usually.The dense fluid that parallel orientation allows the anode surface place to produce passes through anode surface and enters one of groove 607 toward current downflow.Electroplating unit 600 also comprises film supporting component 606.Film supporting component 606 is fastened to base member 604 at its outer perimeter place usually, and comprises and be configured to allow the interior region of fluid by it.Film 608 is upheld and is being supported on 606, and operation separates the catholyte liquid chamber and the anolyte chamber of electroplating unit with fluid ground.Film supporting component 606 can comprise near the O ring type sealing the circumference that is positioned at film, and wherein sealing is configured to prevent that fluid from supporting the opposite side of an effluent of the film on 606 to this film from being fastened on film.Porous ceramics dish member and be configured to produce fluidic base layer stream or even mobile diffuser plate 610 on the direction of substrate being electroplated normally is positioned in film 608 and by between the galvanized substrate in the unit.That submit on October 9th, 2002, require the U.S. Provisional Patent Application submitted on July 24th, 2002 number 60/398, Application No. 10/,268 345 right of priority, that be entitled as the common transfer of " Electrochemical Processing Cell ", further explained this exemplary plating unit in 284, both all are incorporated into this with it by reference in full.
Though illustrated and described in detail several preferred embodiments in conjunction with the present invention's instruction, those skilled in the art can easily still be combined many other of these instructions and be revised embodiment.
Claims (according to the modification of the 19th of treaty)
1. the method for a Direct Electroplating copper on substrate, described substrate comprises the metal barrier that is arranged on the substrate surface, said method comprising the steps of:
The described substrate surface of pre-treatment is with the critical current density of the described metal barrier of process during removing metal oxide layer from described metal barrier and reducing the copper plating; With
To continuously and not have empty copper layer and be plated on the pretreated described substrate surface during described copper is electroplated, wherein the acid electroplating body lotion has the electroplating current density that is equal to or greater than described critical current density.
2. the method for claim 1, wherein said metal barrier comprise the metal of selecting from the group that following metal is formed: ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt).
3. method as claimed in claim 2, the thickness of wherein said metal barrier is less than about 1000 .
4. the method for claim 1 is wherein carried out described copper and is electroplated in 4 hours after described pre-treatment.
5. the method for claim 1, wherein said critical current density reduces along with the increase of the acidity of described plating bath.
6. the method for claim 1, the acidity in the wherein said acid electroplating body lotion is from having the sulfuric acid of about 10g/l to about 300g/l concentration.
7. the method for claim 1, wherein said critical current density is less than about 10mA/cm
2
8. the method for claim 1, wherein said pre-treatment are included in the described substrate of annealing in the treatment chamber that comprises anneal gas.
9. method as claimed in claim 8, wherein said anneal gas is introduced in described treatment chamber with about 1 standard cubic centimeter per minute to the flow rate in about 20 standard Liter Per Minute scopes.
10. method as claimed in claim 8, wherein said anneal gas are heated at the temperature in about 100 ℃ of extremely about 400 ℃ scopes.
11. method as claimed in claim 8, wherein said anneal gas are pressurized to about 5mTorr to the interior pressure of the scope of about 1500Torr.
12. method as claimed in claim 8, wherein said annealing continued the about 2 seconds time length to about 1 hour scope.
13. the method for claim 1, wherein said annealing continue to be shorter than about 1 hour.
14. the method for claim 1 is wherein carried out described pre-treatment in the single wafer annealing chamber of one.
15. the method for claim 1, wherein said pre-treatment comprises cathode treatment, and described cathode treatment comprises described substrate is exposed to and contains acid bath liquid.
16. method as claimed in claim 15, the wherein said acid bath liquid that contains has the acid concentration of about 10g/l to about 100g/l.
17. method as claimed in claim 16, wherein with about 0 volt to about-0.5 volt the scope current potential or with at about 0.05mA/cm
2To about 1mA/cm
2Scope in current density carry out described cathode treatment.
18. method as claimed in claim 15, the wherein said acid bath liquid that contains comprises sulfuric acid.
19. method as claimed in claim 16, wherein said acid concentration is in the scope of 10g/l between about 50g/l.
Claims (20)
1. the method for a Direct Electroplating copper on substrate, described substrate has the VIII family metal level on substrate surface, said method comprising the steps of:
The described substrate surface of pre-treatment is to remove VIII family oxidation on metal surface thing layer and/or the organic surface contaminant on the described substrate surface, the critical current density during reducing to electroplate; With
To continuously and not have empty copper layer with the electroplating current that is equal to or greater than described critical current density in the acid electroplating body lotion is plated on the pretreated described substrate surface.
2. the method for claim 1, wherein said VIII family metal is selected from the group that following metal is formed: ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt).
3. the method for claim 1, the thickness of wherein said VIII family metal is less than about 1000 .
4. the method for claim 1 is wherein carried out described copper and is electroplated in 4 hours after described pre-treatment.
5. the method for claim 1, wherein said critical current density reduces along with the increase of the acidity of described plating bath.
6. the method for claim 1, the acidity in the wherein said acid electroplating body lotion is from having the sulfuric acid of about 10g/l to about 300g/l concentration.
7. the method for claim 1, wherein said critical current density is less than 10mA/cm
2
8. the method for claim 1, wherein by with described substrate have hydrogen-containing gas and/or with the environment of nonreactive one or more gases of VIII family metal in annealing finish the step of the described substrate of pre-treatment.
9. method as claimed in claim 8, the flow rate of wherein said gas at about 1 standard cubic centimeter per minute to about 20 standard Liter Per Minutes.
10. described annealing wherein takes place with the temperature between about 100 ℃ to about 400 ℃ in method as claimed in claim 8.
11. described annealing wherein takes place with the pressure of about 5mTorr between about 1500Torr in method as claimed in claim 8.
12. method as claimed in claim 8, wherein said annealing have the time length between about 2 seconds to about 1 hour.
13. the method for claim 1, wherein the described substrate of pre-treatment is shorter than about 1 hour.
14. the method for claim 1 is wherein carried out described pre-treatment in the single wafer annealing chamber of one.
15. the method for claim 1 is wherein finished the step of the described substrate of pre-treatment by the cathode treatment in containing acid bath liquid.
16. method as claimed in claim 15, the wherein said acid bath liquid that contains has the acid concentration of about 10g/l to about 100g/l.
17. method as claimed in claim 16, wherein with about 0 volt to about-0.5 volt the scope current potential or with at about 0.05mA/cm
2To about 1mA/cm
2Scope in current density carry out described cathode treatment.
18. method as claimed in claim 15, the wherein said acid bath liquid that contains comprises sulfuric acid.
19. method as claimed in claim 16, wherein said acid concentration is in the scope of 10g/l between about 50g/l.
20. the method for claim 1, the copper-plated initial electroplating current that wherein powers in pre-treatment VIII family metallic surface equals described critical current density at least.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57912904P | 2004-06-10 | 2004-06-10 | |
| US60/579,129 | 2004-06-10 | ||
| US11/007,857 | 2004-12-09 |
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| Publication Number | Publication Date |
|---|---|
| CN1965110A true CN1965110A (en) | 2007-05-16 |
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ID=38083496
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580019070 Pending CN1965110A (en) | 2004-06-10 | 2005-06-07 | Method of barrier layer surface treatment to enable direct copper plating on barrier metal |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102859035A (en) * | 2009-09-30 | 2013-01-02 | 东京电子株式会社 | Methods for multi-step copper plating on a continuous ruthenium film in recessed features |
| CN104313657A (en) * | 2014-11-10 | 2015-01-28 | 临安振有电子有限公司 | Electro-deposition device of through hole of HDI printed circuit board |
| CN110233099A (en) * | 2014-03-19 | 2019-09-13 | 应用材料公司 | Electrochemistry electro-plating method |
| CN110416782A (en) * | 2019-08-27 | 2019-11-05 | 问问智能信息科技有限公司 | A kind of charging contact composite structure and preparation method thereof |
| CN111261585A (en) * | 2018-11-30 | 2020-06-09 | 台湾积体电路制造股份有限公司 | Electrochemical plating system and process execution method, method for forming semiconductor structure |
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2005
- 2005-06-07 CN CN 200580019070 patent/CN1965110A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102859035A (en) * | 2009-09-30 | 2013-01-02 | 东京电子株式会社 | Methods for multi-step copper plating on a continuous ruthenium film in recessed features |
| CN110233099A (en) * | 2014-03-19 | 2019-09-13 | 应用材料公司 | Electrochemistry electro-plating method |
| CN110233099B (en) * | 2014-03-19 | 2023-05-16 | 应用材料公司 | Electrochemical plating method |
| CN104313657A (en) * | 2014-11-10 | 2015-01-28 | 临安振有电子有限公司 | Electro-deposition device of through hole of HDI printed circuit board |
| CN111261585A (en) * | 2018-11-30 | 2020-06-09 | 台湾积体电路制造股份有限公司 | Electrochemical plating system and process execution method, method for forming semiconductor structure |
| CN111261585B (en) * | 2018-11-30 | 2023-11-10 | 台湾积体电路制造股份有限公司 | Electrochemical plating system and process execution method, and method for forming semiconductor structure |
| CN110416782A (en) * | 2019-08-27 | 2019-11-05 | 问问智能信息科技有限公司 | A kind of charging contact composite structure and preparation method thereof |
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