CN114182216A - Cu-W-O sputtering target and oxide thin film - Google Patents
Cu-W-O sputtering target and oxide thin film Download PDFInfo
- Publication number
- CN114182216A CN114182216A CN202110422866.1A CN202110422866A CN114182216A CN 114182216 A CN114182216 A CN 114182216A CN 202110422866 A CN202110422866 A CN 202110422866A CN 114182216 A CN114182216 A CN 114182216A
- Authority
- CN
- China
- Prior art keywords
- sputtering target
- thin film
- volume resistivity
- work function
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005477 sputtering target Methods 0.000 title claims abstract description 70
- 239000010409 thin film Substances 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 abstract description 27
- 239000000843 powder Substances 0.000 description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011812 mixed powder Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000009694 cold isostatic pressing Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
Abstract
The invention relates to a Cu-W-O sputtering target and an oxide thin film. A Cu-W-O sputtering target which is a sputtering target comprising tungsten (W), copper (Cu), oxygen (O) and inevitable impurities, wherein the Cu-W-O sputtering target has a volume resistivity of 1.0 x 103Omega cm or less. An oxide thin film is a thin film containing tungsten (W), copper (Cu), oxygen (O) and inevitable impurities, wherein the content ratio of W and Cu satisfies 0.5. ltoreq. W/(Cu + W) < 1 in terms of atomic ratio. The present invention addresses the problem of providing a sputtering target that can form a film having a high work function and has a low volume resistivity.
Description
Technical Field
The present invention relates to a Cu — W-O sputtering target suitable for forming an oxide thin film having a high work function.
Background
ITO (indium tin oxide) is used as a transparent electrode (anode) in a light-emitting element such as an organic electroluminescence (organic EL) element. Holes injected by applying a voltage to the anode are combined with electrons in the light-emitting layer via the hole transport layer. In recent years, in order to improve the charge injection efficiency into the hole transport layer, the use of an oxide having a higher work function than ITO has been studied. For example, in non-exclusiveIn patent document 1, TiO is reported2、MoO2、CuO、NiO、WO3、V2O5、CrO3、Ta2O5、Co3O4The oxide thin film having a high isowork function is used as an oxide thin film in an organic semiconductor device.
WO, as shown in non-patent document 13Has a relatively high work function. The WO3The film can be formed using a sputtering target comprising a tungsten oxide sintered body (patent documents 1 and 2), but in WO3In the case of a single phase, it is difficult to achieve a high density of the sintered body, and DC sputtering is difficult because of high volume resistivity. Thus, patent document 2 discloses a method of producing a compound represented by WO3In which WO is added2Thereby, the density of the sintered body can be increased and the conductivity can be improved, so that DC sputtering can be performed. Patent document 1 discloses that WO is treated in an atmosphere in which oxygen is supplied3The powder is hot pressed to increase the density of the sintered body.
Documents of the prior art
Patent document
[ patent document 1] Japanese patent application laid-open No. 3-150357
[ patent document 2] Japanese patent laid-open publication No. 2013-76163
[ non-patent document ]
[ non-patent document 1] Mark T Greiner and Zheng-Hong Lu, "Thin-Film metals in organic semiconductor devices: the electronic structures, work functions and interfaces ", NPG Asia Materials (2013)5, e55,19July 2013
Disclosure of Invention
Problems to be solved by the invention
As described above, an oxide film having a high work function is desired for a film constituting an organic semiconductor device such as an organic EL device. As a material exhibiting a high work function, WO can be cited3Etc. but in the formation of WO3For example, in the case of a film, since the volume resistivity of a sputtering target used for film formation is high, there is a problem that DC sputtering which enables high-speed film formation cannot be performed. Therefore, the invention aims to solveThe above problems are solved, and an object of the present invention is to provide a sputtering target which can form a film having a high work function and has a low volume resistivity.
Means for solving the problems
The present invention has been made to solve the above problems, and an aspect of the present invention that can solve the above problems is a Cu-W-O sputtering target including tungsten (W), copper (Cu), oxygen (O), and inevitable impurities, wherein the Cu-W-O sputtering target has a volume resistivity of 1.0 × 103Omega cm or less.
Effects of the invention
According to the present invention, the following excellent effects are obtained: the sputtering target is a sputtering target capable of forming a film having a high work function, and can be DC sputtered because of its low volume resistivity, thereby enabling high-speed film formation.
Detailed Description
As described above, WO3Having a high work function, but in WO3In the case of a single phase, it is difficult to produce a sputtering target having a low volume resistivity that can be DC sputtered. In addition, when another oxide material having a high work function (for example, CuO single phase) is used, the volume resistivity is high, and DC sputtering is difficult. The present inventors have conducted intensive studies to solve such problems, and as a result, have obtained the following findings: by making CuO and WO3The mixed system of (3) can provide a sputtering target having a low volume resistivity, which can be DC sputtered while maintaining a high work function, and thus the present invention has been completed.
The sputtering target of the embodiment of the present invention (referred to as Cu-W-O sputtering target) contains tungsten (W), copper (Cu), oxygen (O) and inevitable impurities, and has a volume resistivity of 1.0 × 103Omega cm or less. If the volume resistivity of the sputtering target is 1.0X 103And omega cm or less, DC sputtering can be performed, and thus high-speed film formation can be achieved. The volume resistivity is preferably 1.0X 102Omega cm or less. This enables more stable high-speed film deposition by DC sputtering.
The sputtering target of the present embodiment contains W, Cu, O and unavoidable impurities, and the content ratio of W to Cu is preferably W/(Cu + W) ≧ in terms of atomic ratio0.5. When W/(Cu + W) < 0.5, the volume resistivity may be high, and a desired high work function may not be obtained. W/(Cu + W) ≥ 0.7 is preferable, W/(Cu + W) ≥ 0.8 is more preferable, and W/(Cu + W) ≥ 0.9 is even more preferable. In addition, when WO3In the case of single phase, the sputtering target has a high volume resistivity as described above, and is set to W/(Cu + W) < 1. The inevitable impurities are impurities mixed in raw materials, production processes, and the like, and may be contained in an amount not particularly affecting characteristics such as work function, and it is not particularly problematic as long as the inevitable impurities are 0.1 wt% or less.
The relative density of the sputtering target of the present embodiment is preferably 95% or more. The relative density is preferably 98% or more. Such a high-density sputtering target can prevent cracking and breakage during sputtering, and can reduce particles during film formation. In addition, the relative density of the sputtering target also correlates with the volume resistivity, and as the value of the relative density becomes lower, the volume resistivity tends to become higher. Therefore, in order to reduce the volume resistivity, it is necessary to increase the relative density by strictly adjusting the manufacturing method and manufacturing conditions of the sputtering target in addition to the content ratio of W and Cu in the sputtering target.
The sputtering target according to one embodiment of the present invention has a work function of 4.3eV or more. By using such a sputtering target having a high work function, a film having a high work function can be produced. Such a film having a high work function can improve the charge injection efficiency into the hole transport layer in an organic semiconductor device such as an organic EL or an organic solar cell, and can be expected to improve the light emission efficiency, the conversion efficiency, and the like.
The following describes a method for manufacturing a sputtering target according to the present embodiment. However, it is obvious that the following production conditions and the like are not limited to the disclosed ranges, and some omission and modification may be made.
Preparation of tungsten oxide (WO)3) Powder and copper oxide (CuO) powder were used as raw material powders, and these raw material powders were weighed so as to achieve a desired composition ratio. As copper oxide, Cu may be used in addition to CuO2O, and the like. Next, wet grinding is performed using zirconia beads having a ball diameter of 0.5mm to 3.0 mm. However, the device is not suitable for use in a kitchenThen, the resulting mixture was pulverized until the median of the particle diameters reached 0.1 to 5.0. mu.m, followed by granulation. Next, the obtained granulated powder is subjected to press molding. The press molding is preferably at 300kgf/cm2～400kgf/cm2Under the pressing pressure of (3). Then, Cold Isostatic Pressing (CIP) is performed. The cold isostatic pressing is preferably 1000kgf/cm2～2000kgf/cm2CIP pressure of (a). Subsequently, the obtained molded body is sintered under atmospheric pressure in an oxygen gas flow for 10 to 20 hours. In this case, the sintering temperature is preferably set to 900 ℃ or higher and 950 ℃ or lower. When the sintering temperature is less than 900 ℃, a sintered body of high density cannot be obtained, on the other hand, when the sintering temperature is equal to or more than 950 ℃, as WO3CuWO of composite oxide with CuO4Reacts with the sintered member of alumina and melts, and is therefore not preferred. Then, the obtained sintered body is cut, polished, or the like to be shaped into a target, whereby a sputtering target can be produced. When hot press sintering is used, CuO may be reduced to Cu due to the sintered member of carbon, which may increase the consumption of the member.
In the present specification, various physical properties of a sputtering target and the like are analyzed by the following measurement methods.
(composition of sputtering target and film)
The device comprises the following steps: SPS3500DD manufactured by SII Corp
The method comprises the following steps: ICP-OES (high frequency inductively coupled plasma emission spectrometry)
(composition of film)
The device comprises the following steps: JXA-8500F manufactured by JEOL corporation
The method comprises the following steps: EPMA (Electron Probe microanalyzer)
Acceleration voltage: 5keV to 10keV
Irradiation current: 2.0X 10-7A～2.0×10-8A
Diameter of the probe: 10 μm
The 5 points were selected as the smooth film-formed portions where no dust or the like was adhered and the substrate surface could not be seen, point analysis was performed, and the average composition thereof was calculated.
(volume resistivity of sputtering target)
For the volume resistivity of the sputtering target, 5 points (1 point at the center and 4 points near the outer periphery) were measured on the surface of the sputtering target, and the average value of these was used. The following apparatus was used for the measurement.
The device comprises the following steps: resistivity measuring instrument sigma-5 + manufactured by NPS company
The method comprises the following steps: constant current application mode
The method comprises the following steps: direct current four-probe method
(relative Density of sputtering targets)
Relative density (%) ═ archimedes density/true density × 100
Archimedes density: a piece was cut out from the sputtering target, and the density was calculated from the piece using archimedes' method.
True density: atomic ratios of Cu and W were calculated from elemental analyses, and the weight of Cu in terms of CuO was defined as a (wt%) and the weight of W in terms of WO based on the atomic ratios3B (wt%) is the converted weight, and CuO and WO are added3Is set as dCuO、dWO3Calculating the true density (g/cm)3)＝100/(a/dCuO+b/dWO3). The theoretical density d of CuOCuO＝6.31g/cm3，WO3Theoretical density d ofWO3＝7.16g/cm3。
(with respect to work function)
For the bulk (sputtering target), length: 20mm, width: 10mm, thickness: 5mm to 10 mm. The measurement surface was polished with a 2000-mesh sandpaper. Further, a sample of 20mm × 20mm obtained by forming a film on an Si substrate was prepared as a sputtered film, and the measurement was performed under the following conditions. Note that the work function measurement result does not depend on the size of the sample. Further, when the surface is insufficiently polished without polishing the measurement surface or by polishing with a low-mesh sandpaper, the work function may not be accurately measured, and the value may be measured to be high.
The method comprises the following steps: photoelectron spectroscopy in air
The device comprises the following steps: AC-5 device manufactured by riken counter, Inc
Conditions are as follows: range of work functions that can be measured: 3.4 eV-6.2 eV
Power of light source: 2000W
[ examples ]
The following description will be made based on examples and comparative examples. It should be noted that the present embodiment is only an example, and is not limited to this example. That is, the present invention is limited only by the claims and includes various modifications other than the examples included in the present invention.
(example 1)
Preparing CuO powder and WO3Powder, in the weight ratio CuO: WO350: these powders were weighed at a ratio of 50 (mol%). Subsequently, the resultant was subjected to wet ball mill mixing and pulverization using 3.0mm zirconia beads for 24 hours to obtain a mixed powder having a median particle diameter of 0.8 μm or less. Then, the pressure on the surface was 400kgf/cm2Under the condition of (1), the mixed powder was pressurized and then pressurized at a pressure of 1800kgf/cm2CIP was performed under the conditions of (1) to prepare a molded article.
Next, the sintered body was sintered under atmospheric pressure at a sintering temperature of 940 ℃ for 10 hours in an oxygen gas flow to produce a sintered body. Then, the sintered body is machined to finish the sintered body into the shape of a sputtering target.
The sputtering target obtained in example 1 was evaluated, and as a result, the relative density was 103.3%, and the volume resistivity was 1.0X 103Omega cm. In addition, work functions were measured for the sputtering target, and as a result, work functions as high as 4.5eV were obtained. The above results are shown in table 1. The sputtering target was analyzed for its composition, and as a result, it was confirmed that there was almost no change in the ratio of the raw material charged.
(examples 2 to 5)
Preparing CuO powder and WO3Powders were weighed to give the molar ratios shown in Table 1The molar ratio is. Subsequently, the resultant was subjected to wet ball mill mixing and pulverization using 3.0mm zirconia beads for 24 hours to obtain a mixed powder having a median particle diameter of 0.8 μm or less. Then, the pressure on the surface was 400kgf/cm2Under the condition of (1), the mixed powder was pressurized and then pressurized at a pressure of 1800kgf/cm2CIP was performed under the conditions of (1) to prepare a molded article.
Next, the sintered body was sintered under atmospheric pressure at a sintering temperature of 940 ℃ for 10 hours in an oxygen gas flow to produce a sintered body. Then, each sintered body is machined to finish the shape of the sputtering target.
The sputtering targets of examples 2 to 5 all had a relative density of 99% or more and a volume resistivity of 1.0X 103Omega cm or less. Further, the work functions of the sputtering targets were measured, and all the results were as high as 4.5 eV. The sputtering target was analyzed for its composition, and as a result, it was confirmed that there was almost no change in the ratio of the sputtering target to the raw material charged.
Comparative example 1
In comparative example 1, only CuO powder was used, and WO was not used3And (3) powder. The Cu powder was subjected to 24-hour wet ball mill mixing and pulverization using 3.0mm zirconia beads, thereby obtaining a mixed powder having a median particle diameter of 0.8 μm or less. Then, the pressure on the surface was 400kgf/cm2Under the condition of (1), the mixed powder was pressurized and then pressurized at a pressure of 1800kgf/cm2CIP was performed under the conditions of (1) to prepare a molded article.
Subsequently, the sintered body was sintered under atmospheric pressure at a sintering temperature of 950 ℃ for 10 hours in an oxygen gas flow to produce a sintered body. Then, the sintered body is machined to finish the sintered body into the shape of a sputtering target.
The sputtering target obtained in comparative example 1 was evaluated, and as a result, the relative density was 98.3%, and the volume resistivity was 3.3X 105Omega cm. Further, the work function of the sputtering target was measured, and the result was 4.2 eV. The sputtering target was analyzed for its composition, and as a result, it was confirmed that there was almost no change in the ratio of the sputtering target to the raw material charged.
Comparative examples 2 and 3
In comparative examples 2 and 3, only WO was used3Powder, CuO powder was not used. WO 3.0mm zirconia beads3The powders were subjected to 24-hour wet ball mill mixing and pulverization to obtain a mixed powder having a median particle diameter of 0.8 μm or less. Then, the pressure on the surface was 400kgf/cm2Under the condition of (1), the mixed powder was pressurized and then pressurized at a pressure of 1800kgf/cm2CIP was performed under the conditions of (1) to prepare a molded article.
Next, the sintering temperature was set to 1100 ℃ (comparative example 2) and 940 ℃ (comparative example 3) in an oxygen gas flow, and the sintered body was prepared by sintering at atmospheric pressure for 10 hours. Then, the sintered body is machined to finish the sintered body into the shape of a sputtering target.
Evaluation of the sputtering targets obtained in comparative examples 2 and 3 revealed that the relative densities were 95% or less and the volume resistivities were 1.0X 10 or more3Omega cm. Further, the work function of the sputtering target was measured, and the result was 4.4 eV. The sputtering target was analyzed for its composition, and as a result, it was confirmed that there was almost no change in the ratio of the sputtering target to the raw material charged.
Comparative example 4
Preparing CuO powder and WO3Powder, in the weight ratio CuO: WO330: the powders were weighed at a ratio of 70 (mol%). Subsequently, the resultant was subjected to wet ball mill mixing and pulverization using 3.0mm zirconia beads for 24 hours to obtain a mixed powder having a median particle diameter of 0.8 μm or less. The pressure on the surface was 400kgf/cm2Under the condition of (1), the mixed powder was pressurized and then pressurized at a pressure of 1800kgf/cm2CIP was performed under the conditions of (1) to prepare a molded article.
Subsequently, the sintered body was sintered under atmospheric pressure at a sintering temperature of 850 ℃ for 10 hours in an oxygen gas flow to produce a sintered body. Then, the sintered body is machined to finish the sintered body into the shape of a sputtering target.
The sputtering target obtained in comparative example 4 was evaluated, and the resulting volume resistivity was 3.1 × 104Ω·cm。
Next, sputtering deposition was performed using the sputtering target of example 3. The film forming conditions are as followsThe following is described. The work function of the obtained sputtered film was measured, and the result was 4.6eV in Ar gas and + 6% O in Ar gas2The lower is 4.8eV, and the desired high work function is obtained. The composition analysis of the sputtered film revealed that the ratio was almost unchanged from the ratio at the time of raw material addition.
(film Forming conditions)
The device comprises the following steps: SPL-500 sputtering device manufactured by CANON ANELVA
Substrate: silicon substrate
Film formation power density: 1.0W/cm2
Film forming atmosphere: ar or Ar + 6% O2
Gas pressure: 0.5Pa
Film thickness: 50nm
Industrial applicability
The Cu — W-O sputtering target according to the embodiment of the present invention has a low volume resistivity, can be DC sputtered, has a high relative density, and can be used at a practical and commercial level without causing cracking or chipping of the target during film formation. The present invention is particularly useful for forming a transparent electrode in a light-emitting element such as an organic electroluminescent element.
Claims (6)
1. A Cu-W-O sputtering target which is a sputtering target comprising tungsten (W), copper (Cu), oxygen (O) and inevitable impurities, wherein the Cu-W-O sputtering target has a volume resistivity of 1.0 x 103Omega cm or less.
2. The Cu-W-O sputtering target according to claim 1, wherein the Cu-W-O sputtering target has a relative density of 95% or more.
3. The Cu-W-O sputtering target according to claim 1 or 2, wherein the content ratio of W and Cu satisfies 0.5. ltoreq. W/(Cu + W) < 1 in terms of atomic ratio.
4. The Cu-W-O sputtering target according to any one of claims 1 to 3, wherein the Cu-W-O sputtering target has a work function of 4.3eV or more.
5. An oxide thin film is a thin film containing tungsten (W), copper (Cu), oxygen (O) and inevitable impurities, wherein the content ratio of W and Cu satisfies 0.5. ltoreq. W/(Cu + W) < 1 in terms of atomic ratio.
6. The oxide thin film according to claim 5, wherein the oxide thin film satisfies a work function of 4.5eV or more.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020154239A JP7162647B2 (en) | 2020-09-15 | 2020-09-15 | Cu-W-O sputtering target and oxide thin film |
| JP2020-154239 | 2020-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114182216A true CN114182216A (en) | 2022-03-15 |
Family
ID=80601322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110422866.1A Pending CN114182216A (en) | 2020-09-15 | 2021-04-20 | Cu-W-O sputtering target and oxide thin film |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7162647B2 (en) |
| KR (1) | KR20220036347A (en) |
| CN (1) | CN114182216A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108930015A (en) * | 2016-03-31 | 2018-12-04 | 捷客斯金属株式会社 | Zinc-oxide-based (IZO) sputtering target of indium oxide-and its manufacturing method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2693599B2 (en) | 1989-11-06 | 1997-12-24 | 日本タングステン株式会社 | Target and its manufacturing method |
| KR20130007649A (en) | 2005-02-16 | 2013-01-18 | 매사추세츠 인스티튜트 오브 테크놀로지 | Light emitting device including semiconductor nanocrystals |
| JP5169888B2 (en) | 2009-02-04 | 2013-03-27 | 住友金属鉱山株式会社 | Composite tungsten oxide target material and manufacturing method thereof |
| JP2011084804A (en) | 2009-09-18 | 2011-04-28 | Kobelco Kaken:Kk | Metal oxide-metal composite sputtering target |
| US9202822B2 (en) | 2010-12-17 | 2015-12-01 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and manufacturing method thereof |
| JP2013076163A (en) | 2011-09-15 | 2013-04-25 | Mitsubishi Materials Corp | Sputtering target and method for manufacturing the same |
| KR102420787B1 (en) | 2017-10-20 | 2022-07-13 | 엘지디스플레이 주식회사 | Light emitting diode applying anisotropic nano rod and light emitting apparatus having thereof |
| JP6377230B1 (en) | 2017-10-20 | 2018-08-22 | デクセリアルズ株式会社 | Mn-W-Cu-O-based sputtering target and method for producing the same |
-
2020
- 2020-09-15 JP JP2020154239A patent/JP7162647B2/en active Active
-
2021
- 2021-04-20 CN CN202110422866.1A patent/CN114182216A/en active Pending
- 2021-09-09 KR KR1020210120384A patent/KR20220036347A/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108930015A (en) * | 2016-03-31 | 2018-12-04 | 捷客斯金属株式会社 | Zinc-oxide-based (IZO) sputtering target of indium oxide-and its manufacturing method |
Non-Patent Citations (2)
| Title |
|---|
| LE CHEN.ET.AL.: "Amorphous copper tungsten oxide with tunable band gaps", JOURNAL OF APPLIED PHYSICS, no. 108, 16 August 2010 (2010-08-16), pages 043502 - 1 * |
| YUANCHENG CHANG.ET.AL.: "Effect of Thermal Treatment on the Crystallographic, Surface Energetics, and Photoelectrochemical Properties of Reactively Cosputtered Copper Tungstate for Water Splitting", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》, no. 115, 14 November 2011 (2011-11-14), pages 25490 - 25495 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220036347A (en) | 2022-03-22 |
| JP7162647B2 (en) | 2022-10-28 |
| TW202212595A (en) | 2022-04-01 |
| JP2022048423A (en) | 2022-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111164233B (en) | Oxide sputtering target, method for producing same, and oxide thin film formed using same | |
| US9773652B2 (en) | MgO target for sputtering | |
| TWI422696B (en) | Oxide vapor deposition material and transparent conductive film | |
| US9346715B2 (en) | Lanthanum hexaboride sintered body, target and lanthanum hexaboride film each comprising same, and process for production of the sintered body | |
| JP2012052227A (en) | Method for manufacturing sputtering target, and sputtering target | |
| JP5334246B2 (en) | Ion plating target for zinc oxide thin film production | |
| JP5082927B2 (en) | Method for producing ZnO vapor deposition material | |
| KR100948557B1 (en) | ???2 sputtering target and process for producing same | |
| JP2011074479A (en) | Target for ion plating for producing zinc oxide-based transparent conductive thin film, and zinc oxide-based transparent conductive thin film | |
| JPWO2007069415A1 (en) | Sintered body for vacuum deposition | |
| CN114182216A (en) | Cu-W-O sputtering target and oxide thin film | |
| CN112912355A (en) | Sintered body | |
| TWI837462B (en) | Cu-W-O sputtering target and oxide film | |
| JP4962356B2 (en) | ZnO vapor deposition material and ZnO film formed thereby | |
| TWI750469B (en) | Target and process for producing a target | |
| JP7436409B2 (en) | Oxide sputtering target, its manufacturing method, and oxide thin film | |
| KR102274149B1 (en) | Sputtering target member, method for producing sputtering target member, sputtering target, sputtered film, method for producing sputtered film, film body, laminate structure, and organic el device | |
| JP6160396B2 (en) | Method for producing transparent conductive film | |
| TW201326082A (en) | Sintered oxide article and method for manufacture thereof, and transparent oxide conductive film | |
| JP2008075126A (en) | Dysprosium oxide-containing oxide target |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |