US20040018728A1 - Chemical mechanical polishing solution for platinum - Google Patents
Chemical mechanical polishing solution for platinum Download PDFInfo
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- US20040018728A1 US20040018728A1 US10/460,695 US46069503A US2004018728A1 US 20040018728 A1 US20040018728 A1 US 20040018728A1 US 46069503 A US46069503 A US 46069503A US 2004018728 A1 US2004018728 A1 US 2004018728A1
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- platinum
- interlayer insulating
- solution
- insulating film
- cmp
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 238000005498 polishing Methods 0.000 title claims abstract description 41
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 38
- 239000000126 substance Substances 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 75
- 239000011229 interlayer Substances 0.000 claims description 50
- 239000002002 slurry Substances 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000007517 polishing process Methods 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 2
- -1 tetramethyl ammoniumhydride Chemical compound 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
Definitions
- a solution for platinum abbreviated as “Pt” chemical mechanical polishing (abbreviated as “CMP”) containing an alkali aqueous solution and an oxidizer is disclosed. More specifically, a method for forming Pt patterns including using the above Pt-CMP solution is disclosed which can improve a polishing rate and polishing characteristics of Pt used as a lower electrode of a metal capacitor.
- Pt platinum
- CMP chemical mechanical polishing
- Platinum is a noble metal which is chemically and mechanically stable, and is an essential material used in fabricating high performance semiconductor devices.
- platinum (Pt) has been recently used as a lower electrode in DRAM devices. The lower electrode is created while forming metal layer/insulating film/metal layer-type capacitors through an electro-deposition process.
- the slurry for a metal CMP process with a strong acidity of pH 2 ⁇ 4 contains an abrasive such as alumina (Al 2 O 3 ) or manganese oxide (MnO 2 ) and an oxidizer such as hydrogen peroxide (H 2 O 2 ) or ferric nitrate (Fe(NO 3 ) 2 ) as a first additive, using distilled water or ultra pure water. Further, a small amount of surfactant or dispersing agent may be added to improve CMP slurry properties.
- the Pt layers may be separated from the interlayer insulating film because the Pt layer has poor adhesion to the interlayer insulating film.
- dishing and erosion effects are generated on the Pt layer adjacent to the interlayer insulating film.
- the abrasive included in the slurry can severely scratch the interlayer insulating film, and impurities such as the slurry grounds can remain on the Pt layer. Therefore, the properties of the resultant device are compromised.
- Solutions for platinum CMP are disclosed which can improve the polishing speed of platinum under a low polishing pressure and reduce dishing of the platinum layer and scratches on the interlayer insulating film.
- FIG. 1 is a cross-sectional view illustrating a Pt electrode formed using a disclosed solution.
- FIG. 2 is a graph illustrating a current dependent on a potential of Pt formed using a disclosed solution.
- FIGS. 3 a through 3 d are graphs illustrating growth rate of Pt oxide layer under various solutions.
- CMP solutions containing an oxidizer in an alkali aqueous solution are disclosed.
- the CMP solutions can be used for polishing and planarizing Pt.
- the alkali aqueous solution contains alkali compounds selected from the group consisting of sodium hydride, potassium hydride, tetramethyl ammoniumhydride, tetraalkyl ammonium hydride and mixtures thereof. Potassium hydride (KOH) is preferably used.
- the alkali aqueous solution preferably has a concentration ranging from 0.01 M to 10 M, and preferably ranging from 0.1 M to 5 M.
- Examples of the oxidizer are any of the compounds which make Pt atoms lose the electrons to oxidize the Pt.
- Fe(NO 3 ) 2 is used, and preferably H 2 O 2 as the oxidizer.
- the oxidizer is present in concentration ranging from 1 vol % to 50 vol % to the alkali aqueous solution, and more preferably, ranging from 1 vol % to 10 vol % to the alkali aqueous solution.
- the CMP solution comprising the alkali aqueous solution and the oxidizer maintains its pH ranging from 8 to 14and more preferably ranging from 10 to 14.
- the disclosed Pt-CMP solution changes the physical and chemical properties of the surface of Pt layer by way of the alkali aqueous solution and the oxidizer. That is, using the disclosed CMP solution, the binding strength and compactness between Pt atoms are decreased. Consequently, the oxidation speed of the Pt layer surface increases.
- the disclosed Pt-CMP solution includes no abrasive and thus decreases scratches generated on the exposed interlayer insulating film.
- a disclosed method for forming a platinum pattern comprises:
- Step (c) may further comprise performing a primary CMP process polishing the Pt layer using the disclosed CMP solution until interlayer insulating film is exposed and performing a secondary CMP process polishing the exposed interlayer insulating film using slurry for an interlayer insulating film.
- the Pt-formed semiconductor substrate is contacted with a polishing pad of a rotary table of a CMP system under pressure. Then, the disclosed Pt-CMP solution is supplied to an interface between the polishing pad and the Pt layer, and the Pt layer is polished.
- the CMP process is performed under a pressure ranging from 1 to 3 psi, at a table revolution of a rotary type system ranging from 10 to 80 rpm, and at a linear table speed ranging from 100 to 600 fpm depending upon the polishing speed of the Pt layer and the polishing property of the interlayer insulating film.
- a touch polishing process of interlayer insulating film pattern is performed at the time the interlayer insulating film is exposed, using CMP slurry for interlayer insulating film.
- the touch polishing process is a buffering step to prevent the Pt layer from dishing generated by the difference in polishing selectivity between the Pt layer and the interlayer insulating film of the primary CMP process.
- the polishing conditions are similar to that of the primary CMP process.
- polishing pads can be used in the above CMP process according to the polishing properties of the Pt layer.
- a soft pad can be used to raise uniformity of the polished layer and a hard pad can be used to improve planarity.
- a stack pad laminated with the above two pads or the combination of the above pads can be also used.
- a metal adhesion layer such as titanium (Ti) or titanium nitride (TiN) can be further formed on the top surface of the interlayer insulating film pattern before forming Pt layer so as to improve adhesiveness of the Pt layer.
- a disclosed method for forming a platinum pattern comprises:
- the interlayer insulating pattern is an oxide pattern, and the Pt pattern is used as the lower electrode pattern.
- the Pt-formed semiconductor substrate is contacted to a polishing pad of a rotary table of a CMP system under pressure. Then, the disclosed Pt-CMP solution is supplied to an interface of the polishing pad and the Pt layer, and the Pt layer is polished.
- the primary CMP process is performed under a pressure ranging from 1 to 3 psi, at a table revolution of a rotary type system ranging from 10 to 80 rpm, and at a linear table speed ranging from 100 to 600 fpm depending upon the polishing speed of the Pt layer and the polishing property of the interlayer insulating film.
- the exposed metal adhesion layer is polished using metal CMP slurry until the interlayer insulating film is exposed.
- a touch polishing process of interlayer insulating film is performed at the time the interlayer insulating film is exposed, using CMP slurry for interlayer insulating film.
- the touch polishing process is a buffering step to prevent the Pt layer from dishing generated by the difference in polishing selectivity between the metal layer and the interlayer insulating film.
- conditions of the secondary CMP process and the tertiary CMP process are similar to that of the primary CMP process.
- a metal adhesion layer 3 is formed on a semiconductor substrate 1 , and an interlayer insulating film (not shown) is sequentially formed thereon.
- a general lithography is performed on a predetermined portion of the interlayer insulating film where the lower electrode is formed. Then, an opening portion to expose the metal adhesion layer 3 and an interlayer insulating film pattern 5 are formed.
- a CMP process is performed to form a Pt pattern 7 as a lower electrode.
- a soft pad, a hard pad, a stack pad laminated with the above two pads or the combination of the above pads can be used for the polishing pads used in the primary and the secondary CMP processes.
- KOH 1 mole
- H 2 O 2 was added to be present in a final concentration of 2 vol % to the resulting solution.
- the resulting solution was further stirred for more than 10 minutes until it was completely mixed and stabilized, thereby obtaining the Pt-CMP solution.
- a Pt layer was dipped in 1 M KOH aqueous solution containing 2 vol % H 2 O 2 prepared in the above Example 1 and other 1 M KOH aqueous solution not containing the oxidizer. Then, a voltage was applied to the two solutions, and a current generated on the surface of the Pt layer was compared.
- FIG. 2 shows the current dependent on a potential of the Pt layer formed using a disclosed solution.
- FIGS. 3 a through 3 d show concentrations of elements such as Pt, O and C to polishing time.
- the concentration of the oxide layer formed on the Pt surface is higher than that of the Pt.
- the concentration of the oxide layer decreases, and the concentration of the polished Pt increases.
- the thickness ( ⁇ ) where the oxide layer penetrates into the Pt surface in various kinds of slurries is obtained by measuring polishing time until the oxide layer is removed by the polishing process.
- the slurry for oxidizing most the Pt surface was known by the polishing time.
- Table 1 shows the results as follows. TABLE 1 Thickness of oxide layer penetrating into Pt dipping condition Pt surface ( ⁇ ) Common slurry for metal 100 KOH aqueous solution 75 Disclosed KOH aqueous solution 225 containing oxidizer Exposure to air 75
- the disclosed CMP process is performed by using the disclosed platinum CMP solution containing the oxidizer in the alkali aqueous solution, which improves the polishing speed of platinum under a low pressure and reduces dishing of the Pt layer.
- the disclosed solution decreases scratches generated in the interlayer insulating film because the solution does not contain an abrasive like conventional slurries for metal. As a result, an improved technique for device isolation and reduction of step coverage is disclosed.
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
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- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
A solution for platinum chemical mechanical polishing is disclosed. Further, a method for forming Pt patterns is disclosed which utilizes the disclosed Pt-CMP solution which contains an alkali aqueous solution and an oxidizer which improves the polishing rate and polishing characteristics of Pt which forms a lower electrode of a metal capacitor.
Description
- 1. Technical Field
- A solution for platinum (abbreviated as “Pt”) chemical mechanical polishing (abbreviated as “CMP”) containing an alkali aqueous solution and an oxidizer is disclosed. More specifically, a method for forming Pt patterns including using the above Pt-CMP solution is disclosed which can improve a polishing rate and polishing characteristics of Pt used as a lower electrode of a metal capacitor.
- 2. Description of the Related Art
- Platinum is a noble metal which is chemically and mechanically stable, and is an essential material used in fabricating high performance semiconductor devices. In addition, platinum (Pt) has been recently used as a lower electrode in DRAM devices. The lower electrode is created while forming metal layer/insulating film/metal layer-type capacitors through an electro-deposition process.
- However, when the Pt layer is electro-deposited, the current is non-uniform due to the geometry and density of the oxide layer that is used for isolation. As a result, the Pt layer is non-uniformly formed and short-circuit is caused.
- In order to solve the above-described problem, after the Pt layer is electro-deposited, a CMP process can be performed on the upper portion of the layer to planarize the Pt layer. However, because the Pt layer has relatively low chemical reactivity, appropriate CMP slurry cannot be provided to polish the Pt during CMP process. Thus, the common slurries intended for other metals such as tungsten or aluminum are employed when polishing platinum.
- The slurries intended for other metals also include chemicals for planarizing of the various metal layers on a silicon substrate. In general, the slurry for a metal CMP process with a strong acidity of
pH 2˜4 contains an abrasive such as alumina (Al2O3) or manganese oxide (MnO2) and an oxidizer such as hydrogen peroxide (H2O2) or ferric nitrate (Fe(NO3)2) as a first additive, using distilled water or ultra pure water. Further, a small amount of surfactant or dispersing agent may be added to improve CMP slurry properties. - Since the polishing speed of Pt layers is very slow, the CMP process is performed for a long period of time under high polishing pressure in order to adequately planarize the Pt.
- As a result, the Pt layers may be separated from the interlayer insulating film because the Pt layer has poor adhesion to the interlayer insulating film. In addition, dishing and erosion effects are generated on the Pt layer adjacent to the interlayer insulating film.
- Moreover, when the Pt layer is polished for a long time under high polishing pressure, the abrasive included in the slurry can severely scratch the interlayer insulating film, and impurities such as the slurry grounds can remain on the Pt layer. Therefore, the properties of the resultant device are compromised.
- Solutions for platinum CMP are disclosed which can improve the polishing speed of platinum under a low polishing pressure and reduce dishing of the platinum layer and scratches on the interlayer insulating film.
- Methods for forming a platinum pattern including CMP process using the above Pt-CMP solution are also disclosed.
- FIG. 1 is a cross-sectional view illustrating a Pt electrode formed using a disclosed solution.
- FIG. 2 is a graph illustrating a current dependent on a potential of Pt formed using a disclosed solution.
- FIGS. 3a through 3 d are graphs illustrating growth rate of Pt oxide layer under various solutions.
- CMP solutions containing an oxidizer in an alkali aqueous solution are disclosed. The CMP solutions can be used for polishing and planarizing Pt.
- The alkali aqueous solution contains alkali compounds selected from the group consisting of sodium hydride, potassium hydride, tetramethyl ammoniumhydride, tetraalkyl ammonium hydride and mixtures thereof. Potassium hydride (KOH) is preferably used. Here, the alkali aqueous solution preferably has a concentration ranging from 0.01 M to 10 M, and preferably ranging from 0.1 M to 5 M.
- Examples of the oxidizer are any of the compounds which make Pt atoms lose the electrons to oxidize the Pt. For example, Fe(NO3)2 is used, and preferably H2O2 as the oxidizer. The oxidizer is present in concentration ranging from 1 vol % to 50 vol % to the alkali aqueous solution, and more preferably, ranging from 1 vol % to 10 vol % to the alkali aqueous solution.
- It is preferable that the CMP solution comprising the alkali aqueous solution and the oxidizer maintains its pH ranging from 8 to 14and more preferably ranging from 10 to 14.
- In order to find out chemical reactivity of the Pt-CMP solution, after a predetermined voltage is externally applied to 1 M KOH aqueous solution containing 2 vol % H2O2 and other 1 M KOH aqueous solution not containing the oxidizer, current obtained by electro-chemical reactions generated on the Pt surface are measured.
- As a result, it is shown that current density of KOH aqueous solution containing the oxidizer is higher than KOH solution not containing the oxidizer when having the same applied potential. Accordingly, it is recognized that Pt layers are more rapidly oxidized by the disclosed Pt-CMP solutions (see FIG. 2).
- When an oxidation speed of the Pt surface exposed to air is compared with that of the Pt surface exposed to (1) a common slurry for metal, (2) KOH aqueous solution not containing the oxidizer and (3) the disclosed Pt-CMP solution containing oxidizer, the Pt surface exposed to the disclosed solution showed the highest concentration of oxygen. As a result, the Pt surface exposed to the disclosed CMP solution has a greater degree of oxidation after the polishing process (see FIGS. 3a through 3 d).
- The disclosed Pt-CMP solution changes the physical and chemical properties of the surface of Pt layer by way of the alkali aqueous solution and the oxidizer. That is, using the disclosed CMP solution, the binding strength and compactness between Pt atoms are decreased. Consequently, the oxidation speed of the Pt layer surface increases.
- In this way, when the Pt surface is oxidized, its hardness is lowered such that the Pt surface is more easily polished. Thus, the polishing speed under the same pressure is faster and the polishing process is easier when the CMP process is performed on the Pt layer using the disclosed solution than when using a common slurry for metal.
- In addition, in comparison with a conventional slurry, the disclosed Pt-CMP solution includes no abrasive and thus decreases scratches generated on the exposed interlayer insulating film.
- A disclosed method for forming a platinum pattern comprises:
- (a) forming an interlayer insulating film pattern having a contact hole on a semiconductor substrate;
- (b) forming a platinum layer on the interlayer insulating film pattern; and
- (c) performing a primary platinum CMP process on an overall surface of the platinum layer with the interlayer insulating film pattern as an etching barrier film using the disclosed Pt-CMP solution.
- Step (c) may further comprise performing a primary CMP process polishing the Pt layer using the disclosed CMP solution until interlayer insulating film is exposed and performing a secondary CMP process polishing the exposed interlayer insulating film using slurry for an interlayer insulating film.
- In the primary CMP process, the Pt-formed semiconductor substrate is contacted with a polishing pad of a rotary table of a CMP system under pressure. Then, the disclosed Pt-CMP solution is supplied to an interface between the polishing pad and the Pt layer, and the Pt layer is polished.
- Here, the CMP process is performed under a pressure ranging from 1 to 3 psi, at a table revolution of a rotary type system ranging from 10 to 80 rpm, and at a linear table speed ranging from 100 to 600 fpm depending upon the polishing speed of the Pt layer and the polishing property of the interlayer insulating film.
- Thereafter, in the secondary CMP process, a touch polishing process of interlayer insulating film pattern is performed at the time the interlayer insulating film is exposed, using CMP slurry for interlayer insulating film. The touch polishing process is a buffering step to prevent the Pt layer from dishing generated by the difference in polishing selectivity between the Pt layer and the interlayer insulating film of the primary CMP process. Here, the polishing conditions are similar to that of the primary CMP process.
- Various types of polishing pads can be used in the above CMP process according to the polishing properties of the Pt layer. For example, a soft pad can be used to raise uniformity of the polished layer and a hard pad can be used to improve planarity. And a stack pad laminated with the above two pads or the combination of the above pads can be also used.
- In addition, a metal adhesion layer such as titanium (Ti) or titanium nitride (TiN) can be further formed on the top surface of the interlayer insulating film pattern before forming Pt layer so as to improve adhesiveness of the Pt layer.
- That is, a disclosed method for forming a platinum pattern comprises:
- (a) forming an interlayer insulating film pattern having a contact hole on a semiconductor substrate;
- (b) forming a metal adhesion layer on the interlayer insulating film pattern;
- (c) forming a platinum layer on the metal adhesion layer;
- (d) performing a primary platinum CMP process on an overall surface of the platinum layer using the disclosed Pt-CMP solution until the metal adhesion layer is exposed;
- (e) performing a secondary a CMP process on the resultant surface using a metal slurry until the interlayer insulating film is exposed; and
- (f) performing a touch-polishing process on the resultant surface using slurry for an interlayer insulating film.
- Preferably, the interlayer insulating pattern is an oxide pattern, and the Pt pattern is used as the lower electrode pattern.
- In the primary CMP process, the Pt-formed semiconductor substrate is contacted to a polishing pad of a rotary table of a CMP system under pressure. Then, the disclosed Pt-CMP solution is supplied to an interface of the polishing pad and the Pt layer, and the Pt layer is polished.
- Here, as described above, the primary CMP process is performed under a pressure ranging from 1 to 3 psi, at a table revolution of a rotary type system ranging from 10 to 80 rpm, and at a linear table speed ranging from 100 to 600 fpm depending upon the polishing speed of the Pt layer and the polishing property of the interlayer insulating film.
- Thereafter, in the secondary CMP process, the exposed metal adhesion layer is polished using metal CMP slurry until the interlayer insulating film is exposed.
- In the tertiary CMP process, a touch polishing process of interlayer insulating film is performed at the time the interlayer insulating film is exposed, using CMP slurry for interlayer insulating film. The touch polishing process is a buffering step to prevent the Pt layer from dishing generated by the difference in polishing selectivity between the metal layer and the interlayer insulating film. Here, conditions of the secondary CMP process and the tertiary CMP process are similar to that of the primary CMP process.
- The above secondary and tertiary CMP slurry for a metal and interlayer insulating film is used the general slurry.
- The disclosed Pt-electrode pattern is shown in FIG. 1.
- Referring to FIG. 1, a
metal adhesion layer 3 is formed on asemiconductor substrate 1, and an interlayer insulating film (not shown) is sequentially formed thereon. - A general lithography is performed on a predetermined portion of the interlayer insulating film where the lower electrode is formed. Then, an opening portion to expose the
metal adhesion layer 3 and an interlayer insulatingfilm pattern 5 are formed. - After a Pt layer (not shown) is electro-deposited on the resultant surface, a CMP process is performed to form a
Pt pattern 7 as a lower electrode. - In the above CMP process comprising the Pt-formed semiconductor substrate is contacted to a polishing pad formed on a rotary table of a CMP system under pressure. Then, the disclosed Pt-CMP solution containing H2O2 present at 1 to 10 vol % in a 0.1 to 5 M KOH aqueous solution is supplied to an interface of the polishing pad and the Pt layer, and the Pt layer is polished. Here, the primary CMP process is performed under a pressure ranging from 1 to 3 psi, at a table revolution of a rotary type system ranging from 10 to 80 rpm, and at a linear table speed ranging from 100 to 600 fpm. Thereafter, in the secondary CMP process, a touch polishing process is performed at the time the interlayer insulating film is exposed, using slurry for interlayer insulating film.
- A soft pad, a hard pad, a stack pad laminated with the above two pads or the combination of the above pads can be used for the polishing pads used in the primary and the secondary CMP processes.
- KOH (1 mole) was added to 1000 mL of ultra pure water to prepare 1 M KOH aqueous solution. The resulting solution was stirred, and H2O2 was added to be present in a final concentration of 2 vol % to the resulting solution. The resulting solution was further stirred for more than 10 minutes until it was completely mixed and stabilized, thereby obtaining the Pt-CMP solution.
- A Pt layer was dipped in 1 M KOH aqueous solution containing 2 vol % H2O2 prepared in the above Example 1 and other 1 M KOH aqueous solution not containing the oxidizer. Then, a voltage was applied to the two solutions, and a current generated on the surface of the Pt layer was compared. FIG. 2 shows the current dependent on a potential of the Pt layer formed using a disclosed solution.
- When a potential was 0.4 E/VAg/Agcl, 1 M KOH aqueous solution not containing the oxidizer had a current density of 1×10−5 Am−2 while 1M KHO solution containing 2 vol % H2O2 had a high current density of about 0.05 Am−2. That is, the Pt surface polished with the disclosed solution was more oxidized than the Pt surface polished with the solution not containing the oxidizer.
- Platinum was dipped and oxidized respectively in (1) a common slurry for metal of
pH 6 using CeO2 as an abrasive (see FIG. 3a), (2) 1 M KOH aqueous solution not containing the oxidizer (see FIG. 3b) and (3) 1 M KHO solution containing 2 vol % H2O2 (see FIG. 3c). Then, the surface of Pt was polished at room temperature using AES (Auger Electron-Spectroscopy) at a speed of 50 Å/min, thereby measuring the time the oxidized portion was polished. - After the Pt layer was exposed to air and oxidized, the surface of Pt was polished at the same speed as described above, thereby measuring the time the oxidized portion was polished (see FIG. 3d).
- FIGS. 3a through 3 d show concentrations of elements such as Pt, O and C to polishing time. At an initial stage of the polishing process, the concentration of the oxide layer formed on the Pt surface is higher than that of the Pt. However, as the polishing process proceeded, it is shown that the concentration of the oxide layer decreases, and the concentration of the polished Pt increases.
- The thickness (Å) where the oxide layer penetrates into the Pt surface in various kinds of slurries is obtained by measuring polishing time until the oxide layer is removed by the polishing process. In other words, the slurry for oxidizing most the Pt surface was known by the polishing time. Table 1 shows the results as follows.
TABLE 1 Thickness of oxide layer penetrating into Pt dipping condition Pt surface (Å) Common slurry for metal 100 KOH aqueous solution 75 Disclosed KOH aqueous solution 225 containing oxidizer Exposure to air 75 - As shown in Table 1, the surface of Pt dipped in the alkali aqueous solution containing the disclosed oxidizer is oxidized the most. Therefore, the polishing speed of the Pt layer is increased due to the oxide layer, thereby improving the polishing speed and effect.
- As discussed earlier, the disclosed CMP process is performed by using the disclosed platinum CMP solution containing the oxidizer in the alkali aqueous solution, which improves the polishing speed of platinum under a low pressure and reduces dishing of the Pt layer. In addition, the disclosed solution decreases scratches generated in the interlayer insulating film because the solution does not contain an abrasive like conventional slurries for metal. As a result, an improved technique for device isolation and reduction of step coverage is disclosed.
Claims (20)
1. A chemical mechanical polishing (CMP) solution for platinum comprising:
an alkali aqueous solution; and
an oxidizer.
2. The solution according to claim 1 , wherein the alkali aqueous solution comprises:
alkali compounds selected from the group consisting of sodium hydride, potassium hydride, tetramethyl ammoniumhydride, tetraalkyl ammonium hydride and mixtures thereof.
3. The solution according to claim 1 , wherein the concentration of alkali aqueous solution ranges from 0.01 M to 10 M.
4. The solution according to claim 1 , wherein the concentration of alkali aqueous solution ranges from 0.1 M to 5 M.
5. The solution according to claim 1 , wherein the oxidizer is H2O2, Fe(NO3)2 or mixtures thereof.
6. The solution according to claim 1 , wherein the oxidizer is present in a concentration ranging from 1 vol % to 50 vol % of the alkali aqueous solution.
7. The solution according to claim 1 , wherein the oxidizer is present in a concentration ranging from 1 vol % to 10 vol % of the alkali aqueous solution.
8. The solution according to claim 1 , wherein the pH of the solution ranges from 8 to 14.
9. The solution according to claim 1 , wherein the pH of the solution ranges from 10 to 14.
10. A method for forming a platinum pattern comprising:
(a) forming an interlayer insulating film pattern having a contact hole on a semiconductor substrate;
(b) forming a platinum layer on the interlayer insulating film pattern; and
(c) performing a platinum CMP process on a surface of the platinum layer with the interlayer insulating film pattern as an etching barrier film using the CMP solution of claim 1 .
11. The method according to claim 10 , further comprising:
performing a touch-polishing process on the surface after step (c) using a slurry for an interlayer insulating.
12. The method according to claim 10 , wherein the interlayer insulating film pattern is an oxide pattern.
13. The method according to claim 10 , wherein the platinum pattern is used as a lower electrode pattern.
14. A method for forming a platinum pattern comprising:
(a) forming an interlayer insulating film pattern having a contact hole on a semiconductor substrate;
(b) forming a metal adhesion layer on the interlayer insulating film pattern;
(c) forming a platinum layer on the metal adhesion layer;
(d) performing a platinum CMP process on an overall surface of the platinum layer using the CMP solution of claim 1 until the metal adhesion layer is exposed;
(e) performing a CMP process on the resultant surface using a metal slurry until the interlayer insulating film is exposed; and
(f) performing a touch-polishing process on the resultant surface using slurry for an interlayer insulating film.
15. The method according to claim 14 , wherein the metal adhesion layer is Ti or TiN.
16. The method according to claim 14 , wherein the interlayer insulating film pattern is an oxide pattern.
17. The method according to claim 14 , wherein the platinum pattern is used as a lower electrode pattern.
18. A platinum (Pt) chemical mechanical polishing (CMP) solution comprising:
a KOH aqueous solution; and
hydrogen peroxide.
19. The Pt CMP solution according to claim 18 , wherein the concentration of KOH aqueous solution ranges from 0.01 M to 10 M, and hydrogen peroxide is present in a concentration ranging from 1 to 50 vol % of the KOH aqueous solution.
20. A method for forming a for forming a platinum pattern comprising:
(a) forming an interlayer insulating film pattern having a contact hole on a semiconductor substrate;
(b) forming a metal adhesion layer on the interlayer insulating film pattern;
(c) forming a platinum layer on the metal adhesion layer;
(d) performing a platinum CMP process on an overall surface of the platinum layer using the CMP solution of claim 18 until the metal adhesion layer is exposed;
(e) performing a CMP process on the resultant surface using a metal slurry until the interlayer insulating film is exposed; and
(f) performing a touch-polishing process on the resultant surface using slurry for an interlayer insulating film.
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US11/493,126 US7470623B2 (en) | 2002-06-19 | 2006-07-26 | Method of forming a platinum pattern |
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KR2002-34376 | 2002-06-19 | ||
KR1020020034376A KR20040000009A (en) | 2002-06-19 | 2002-06-19 | Solution for Platinum-Chemical Mechanical Planarization |
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US11/493,126 Division US7470623B2 (en) | 2002-06-19 | 2006-07-26 | Method of forming a platinum pattern |
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US10/460,695 Abandoned US20040018728A1 (en) | 2002-06-19 | 2003-06-12 | Chemical mechanical polishing solution for platinum |
US11/493,126 Expired - Fee Related US7470623B2 (en) | 2002-06-19 | 2006-07-26 | Method of forming a platinum pattern |
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US (2) | US20040018728A1 (en) |
JP (1) | JP2004080007A (en) |
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Cited By (2)
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US20080020680A1 (en) * | 2006-07-24 | 2008-01-24 | Cabot Microelectronics Corporation | Rate-enhanced CMP compositions for dielectric films |
CN104576351A (en) * | 2013-10-23 | 2015-04-29 | 中芯国际集成电路制造(上海)有限公司 | Chemical and mechanical grinding method |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20050211950A1 (en) * | 2004-03-24 | 2005-09-29 | Cabot Microelectronics Corporation | Chemical-mechanical polishing composition and method for using the same |
KR100713232B1 (en) * | 2006-08-30 | 2007-05-04 | 이정자 | Sprouter |
KR101031180B1 (en) * | 2010-01-13 | 2011-05-03 | 산이건설 주식회사 | Infilled type steel box bridge holder |
US8610280B2 (en) | 2011-09-16 | 2013-12-17 | Micron Technology, Inc. | Platinum-containing constructions, and methods of forming platinum-containing constructions |
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- 2003-06-18 TW TW092116543A patent/TWI253465B/en not_active IP Right Cessation
- 2003-06-18 JP JP2003173535A patent/JP2004080007A/en active Pending
- 2003-06-19 CN CNB031486932A patent/CN1238560C/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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CN1238560C (en) | 2006-01-25 |
TWI253465B (en) | 2006-04-21 |
JP2004080007A (en) | 2004-03-11 |
US20060264052A1 (en) | 2006-11-23 |
KR20040000009A (en) | 2004-01-03 |
CN1475604A (en) | 2004-02-18 |
US7470623B2 (en) | 2008-12-30 |
TW200404885A (en) | 2004-04-01 |
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