CN100449816C - A high work function transparent conductive oxide film electrode and its preparation method - Google Patents
A high work function transparent conductive oxide film electrode and its preparation method Download PDFInfo
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- CN100449816C CN100449816C CNB2005100277886A CN200510027788A CN100449816C CN 100449816 C CN100449816 C CN 100449816C CN B2005100277886 A CNB2005100277886 A CN B2005100277886A CN 200510027788 A CN200510027788 A CN 200510027788A CN 100449816 C CN100449816 C CN 100449816C
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- work function
- transparent conductive
- tungsten
- conductive oxide
- high work
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010408 film Substances 0.000 claims abstract description 56
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 36
- 238000004544 sputter deposition Methods 0.000 claims abstract description 29
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 29
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 9
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims 3
- 239000012495 reaction gas Substances 0.000 claims 2
- -1 IWO two layers Chemical compound 0.000 claims 1
- ZONODCCBXBRQEZ-UHFFFAOYSA-N platinum tungsten Chemical compound [W].[Pt] ZONODCCBXBRQEZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 abstract 1
- QTPKWWJYDWYXOT-UHFFFAOYSA-N [W+4].[O-2].[In+3] Chemical compound [W+4].[O-2].[In+3] QTPKWWJYDWYXOT-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- LYYBDUVEZRFROU-UHFFFAOYSA-N [W].[In] Chemical compound [W].[In] LYYBDUVEZRFROU-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910018011 MK-II Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004402 ultra-violet photoelectron spectroscopy Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明是一种高功函数铂钨共掺氧化铟(In2O3:Pt，W)/掺钨氧化铟(IWO)双层透明导电氧化物薄膜电极及其制备方法。本发明以普通玻璃为基板，利用掺钨金属铟镶嵌靶和铂+掺钨金属铟镶嵌靶，通过反应直流磁控溅射技术，在本发明的工作压强和氧分压、溅射电流和溅射电压的条件下制备具有高功函数透明氧化物In2O3:Pt，W/IWO薄膜电极。所制备的薄膜具有低电阻率、高透射率和高功函数等优良的光电特性。通过掺铂含量和In2O3:Pt，W层厚度调制透明导电氧化物薄膜的功函数。本发明获得的高功函数透明导电氧化物薄膜电极在新型有机光电器件领域具有良好的应用前景。The invention relates to a platinum-tungsten co-doped indium oxide (In 2 O 3 :Pt, W)/tungsten-doped indium oxide (IWO) double-layer transparent conductive oxide film electrode with high work function and a preparation method thereof. The present invention uses ordinary glass as the substrate, utilizes tungsten-doped metal indium mosaic target and platinum + tungsten-doped metal indium mosaic target, and adopts reactive DC magnetron sputtering technology to achieve the working pressure, oxygen partial pressure, sputtering current and sputtering The transparent oxide In 2 O 3 :Pt, W/IWO thin film electrode with high work function was prepared under the condition of emission voltage. The prepared film has excellent photoelectric properties such as low resistivity, high transmittance and high work function. The work function of transparent conductive oxide thin films is modulated by the content of doped platinum and the thickness of In 2 O 3 :Pt, W layer. The transparent conductive oxide film electrode with high work function obtained by the invention has a good application prospect in the field of novel organic photoelectric devices.
Description
Technical field
The invention belongs to Organic Light Emitting Diode (OLEDs) technical field, be specifically related to a kind of high work function transparent conductive oxide film electrode and application response direct current magnetron sputtering process thereof and prepare high work function platinum, tungsten and mix indium oxide (In altogether
2O
3: Pt, W)/mix the method for the double-deck transparent conductive oxide film electrode of tungsten indium oxide (IWO).
Background technology
Organic electroluminescence device (OLEDs) has potential application in a lot of fields owing to have characteristics such as high efficiency, high brightness, wide visual angle, low-power consumption, self-luminous, response speed be fast, has therefore obtained people and has paid close attention to widely.And OLEDs has different requirements to the work function of yin, yang transparency electrode.Electrode material as negative electrode will have the injection that low surface work function is beneficial to electronics; Help improving the injection efficiency in hole when being complementary as the HOMO of its work function of electrode material of anode and anode organic material.And the performance of OLEDs and hole injection process have very confidential relation, use tin-doped indium oxide (ITO) to do the anode of OLEDs usually, and as the ITO of hole injection layer among the OLED, it plays a part crucial to the OLED performance.This is because in the OLED device, the work function of ITO (be typically 4.5～4.7eV) and not matching of organic layer (organic molecule or polymer) ionization gesture (about 5.4eV) cause between anode ITO and the hole transmission layer forming an energy barrier, this energy barrier directly influences the efficiency of transmission in charge carrier (hole).Therefore the electrode material as hole injection layer should have higher work function, reduce even elimination contact berrier, improve the injection efficiency of anode charge carrier to greatest extent, thereby improve the internal quantum efficiency of whole OLEDs, reduce the operating voltage of OLEDs device simultaneously, greatly improve efficient, life-span and the stability of OLEDs device.Therefore count to about 5.4eV as if further improving as the work content of hole injection layer, the injection efficiency in hole can further promote so, and the threshold voltage of device can reduce, and luminous efficiency can be improved.Therefore, the research that preparation has high work function transparent conductive oxide film electrode has very big using value, does not still have the correlative study report at present.
Summary of the invention
The object of the present invention is to provide a kind ofly have industrial production, high work function platinum tungsten that technology stability is good is mixed indium oxide (In altogether
2O
3: Pt, W)/mix double-deck transparent conductive oxide film electrode of tungsten indium oxide (IWO) and preparation method thereof.
The present invention proposes a kind of high work function transparent conductive oxide film electrode, and it is In that this electrode is mixed indium oxide altogether by platinum tungsten
2O
3: it is the two-layer composition of IWO, wherein In that Pt, W/ mix the tungsten indium oxide
2O
3: Pt, W bed thickness 0.1-10nm, IWO bed thickness 50-200nm, its work function is 4.5-5.5eV.
The preparation high work function platinum tungsten that the present invention proposes is mixed indium oxide (In altogether
2O
3: Pt, W)/method of mixing the double-deck transparent conductive oxide film electrode of tungsten indium oxide (IWO) is to utilize the dc magnetron sputtering method of prior art to prepare high work function platinum tungsten to mix indium oxide (In altogether
2O
3: Pt, W)/mix the double-deck transparent conductive film electrode of tungsten indium oxide (IWO).Preparation of the present invention is to be target to mix tungsten indium metal mosaic target and platinum+mix tungsten indium metal mosaic target, with common glass is substrate, substrate temperature 200-380 ℃, by the reaction direct current magnetron sputtering process, make Ar ion beam irradiation target, with target as sputter, at sputtering current 100～250mA, operating pressure in the sputtering voltage 300～600V, reative cell is 2.5 * 10
-1～2.5 * 10
0Pa, O
2The dividing potential drop percentage composition P (O of reacting gas
2) [=P
O2/ (P
O2+ P
Ar] be 2.0～20.0%, under aforementioned preparation condition, at first plate electrically conducting transparent IWO film, sputtering time is 5～30 minutes, plates In then on the IWO film
2O
3: Pt, W film, sputtering time are 1-50 second, adopt the last platinum tungsten with high work function that forms of said method to mix indium oxide (In altogether
2O
3: Pt, W)/mix the double-deck transparent conductive oxide film electrode of tungsten indium oxide (IWO).
The above-mentioned tungsten indium metal mosaic target of mixing, i.e. even damascene tungsten wire in the aperture in the magnetron sputtering area on the metal indium circle target; Above-mentioned platinum+mix tungsten indium metal mosaic target is promptly being mixed even metal platinum filament or the platinized platinum placed on the tungsten indium metal mosaic target; Generally platinum filament or platinized platinum are got final product near tungsten wire place.
The present invention's preparation condition preferably is as follows:
Among the present invention, substrate temperature is 150-380 ℃.
Among the present invention, O
2The dividing potential drop of reacting gas is 10-15%.
Among the present invention, during reaction magnetically controlled DC sputtering plated film, sputtering condition is: sputtering current 120-200mA, sputtering voltage 400-450V.
Among the present invention, the 5-10 minute IWO thin film sputtering time of plating, on the IWO film, plate In then
2O
3: Pt, the sputtering time of W film are 1-40 second.
Among the present invention, by variable conductance valve with O
2Feed reative cell with Ar gas, variable conductance valve is the prior art that the magnetically controlled DC sputtering plated film feeds gas.
The high work function platinum tungsten that the inventive method makes is mixed indium oxide (In altogether
2O
3: Pt, W)/to mix the double-deck transparent conductive oxide film electrode thickness of tungsten indium oxide (IWO) be 50-200nm, can be as required, by control sputter IWO film and In
2O
3: Pt, the W film time is controlled thickness and total film thickness separately.
Experimental result shows, the In that the method for utilization reaction magnetically controlled DC sputtering prepares on common glass substrates
2O
3: Pt, the W/IWO film has the characteristic of high work function, low-resistivity and high visible light transmissivity, and its photoelectric properties can be compared with the ITO product, and its work function (5.5eV) is higher than the work function (4.7eV) of ITO.The inventive method has IP prospecting, and technology stability is good, is that a kind of preparation high work function platinum tungsten is mixed indium oxide (In altogether
2O
3: Pt, W)/mix the double-deck transparent conductive oxide film electrode of tungsten indium oxide (IWO), effective new method of novel photoelectric device premium properties is provided.
Description of drawings
Fig. 1 mixes indium oxide (In altogether for the high work function platinum tungsten of the inventive method preparation
2O
3: Pt, W)/mix the UV photoelectron spectroscopy figure (UPS) of double-deck transparent conductive oxide film of tungsten indium oxide (IWO) and single-layer and transparent conductive oxide IWO film.
Fig. 2 mixes indium oxide (In altogether for high work function platinum tungsten
2O
3: Pt, W)/mix the transmissivity figure of the double-deck transparent conductive oxide film of tungsten indium oxide (IWO).
Fig. 3 mixes indium oxide (In altogether for high work function platinum tungsten
2O
3: Pt, W)/mix double-deck transparent conductive oxide film of tungsten indium oxide (IWO) and ITO, the electrical property comparison diagram of ZAO film.
Embodiment
The specific embodiment of the present invention is as follows:
Embodiment 1, tungsten indium oxide target is mixed in preparation: with purity is that 99.99% In metal melting becomes the circle target, embedding purity in the aperture in the magnetron sputtering area of circle target symmetrically is that 99.99% 4wt% tungsten filament is prepared from, and target diameter is 51mm, and thickness is 2.5mm.Preparation platinum tungsten is mixed the indium oxide target altogether: mixing the Pt sheet of putting into 10wt% on the tungsten indium oxide target uniformly.Substrate is common slide, successively cleans in each 15 minutes through pure water, alcohol and acetone ultrasonic wave.
Substrate temperature: 380 ℃.
The spacing of target and substrate is fixed as 75mm.
Earlier reative cell is evacuated down to before the thin film deposition and is lower than 2 * 10
-3Pa, then by variable conductance valve with O
2Feed reative cell with Ar gas.Operating pressure in the reative cell is 2.5 * 10
-1Pa, sputtering current are 150mA, and sputtering voltage is 500V, control O
2Percentage composition P (the O of reacting gas
2) [=P
O2/ (P
O2+ P
Ar] be 14.0%.Film promptly prepares on the simple glass sheet.
Plating IWO film, sputtering time 8 minutes, film thickness are 120nm; On the IWO film, plate In then
2O
3: Pt, W film, sputtering time are 40 seconds, film thickness is 10nm; Total film thickness is 130nm.
Embodiment 2, and method makes high work function platinum tungsten under the following conditions and mixes indium oxide (In altogether similarly to Example 1
2O
3: Pt, W)/tungsten mixes the double-deck transparent conductive oxide film of indium oxide (IWO): sputtering current is 250mA, and sputtering voltage is 400V, by variable conductance valve with O
2Feed reative cell with Ar gas, the operating pressure in the reative cell is 1.0 * 10
0Pa, and control O
2Percentage composition P (the O of gas
2) be 4.0%.Plating IWO film, sputtering time 6 minutes, film thickness are 90nm; On the IWO film, plate In then
2O
3: Pt, W film, sputtering time are 10 seconds, film thickness is 2nm; Total film thickness is 90nm.
Utilize the thickness d of surface profiler (Kosaka ET3000 type) MEASUREMENTS OF THIN, at room temperature adopt the electric property of (Bio-RadMicroscience HL5500 Hall system) Hall test macro MEASUREMENTS OF THIN.Adopt the crystalline structure of X-ray diffractometer (XRD) (RigakuD/max-rB type, Cu K alpha ray source) analysed film; Adopt atomic force microscope (AFM) (Park Scientific Instrument, AutoProbe CP, USA) surface topography of analysed film; Utilize the content of energy dispersion X ray (EDX) analysed film; Utilize and do the work function that ex situ measures ultraviolet photoelectron spectrum (UPS) analysed film on the VG ESCA-Lab MK-II electron spectrometer, ultraviolet source is He I (hv=21.2eV).
Claims (7)
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| CNB2005100277886A CN100449816C (en) | 2005-07-15 | 2005-07-15 | A high work function transparent conductive oxide film electrode and its preparation method |
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|---|---|
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| CN100449816C true CN100449816C (en) | 2009-01-07 |
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| CN101158049B (en) * | 2007-07-31 | 2010-06-02 | 北京工业大学 | Preparation method of P-type transparent conductive oxide CuAlO2 thin film |
| CN110458478A (en) * | 2019-08-23 | 2019-11-15 | 兰州理工大学 | Job Shop Scheduling Method Based on Discrete Invasive Weed Algorithm |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02151838A (en) * | 1988-12-05 | 1990-06-11 | Tokai Rika Co Ltd | Fully solid-state electrochromic element |
| US6366017B1 (en) * | 1999-07-14 | 2002-04-02 | Agilent Technologies, Inc/ | Organic light emitting diodes with distributed bragg reflector |
| US6875320B2 (en) * | 2003-05-05 | 2005-04-05 | Eastman Kodak Company | Highly transparent top electrode for OLED device |
-
2005
- 2005-07-15 CN CNB2005100277886A patent/CN100449816C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02151838A (en) * | 1988-12-05 | 1990-06-11 | Tokai Rika Co Ltd | Fully solid-state electrochromic element |
| US6366017B1 (en) * | 1999-07-14 | 2002-04-02 | Agilent Technologies, Inc/ | Organic light emitting diodes with distributed bragg reflector |
| US6875320B2 (en) * | 2003-05-05 | 2005-04-05 | Eastman Kodak Company | Highly transparent top electrode for OLED device |
Non-Patent Citations (1)
| Title |
|---|
| Linear Model Application for the Design of TransparentConductive In2O3 Electrodes. A.Axelevitch, ect.IEEE. 1996 * |
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