DE3639508A1 - Transparent, electrically conducting film and method of fabricating it - Google Patents
Transparent, electrically conducting film and method of fabricating itInfo
- Publication number
- DE3639508A1 DE3639508A1 DE19863639508 DE3639508A DE3639508A1 DE 3639508 A1 DE3639508 A1 DE 3639508A1 DE 19863639508 DE19863639508 DE 19863639508 DE 3639508 A DE3639508 A DE 3639508A DE 3639508 A1 DE3639508 A1 DE 3639508A1
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- transparent
- zno
- film
- electrically conductive
- conductive film
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- 238000004519 manufacturing process Methods 0.000 title description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000011787 zinc oxide Substances 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 43
- 239000000758 substrate Substances 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910006404 SnO 2 Inorganic materials 0.000 description 5
- 239000012789 electroconductive film Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- 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
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Non-Insulated Conductors (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Electroluminescent Light Sources (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
Die Erfindung betrifft einen transparenten, elektrisch leitenden Film und ein Verfahren zu seiner Herstellung.The invention relates to a transparent, electrical conductive film and a process for its manufacture.
Transparente, elektrisch leitende Filme besitzen hohe elektrische Leitfähigkeit und Transparenz im sichtbaren Bereich und werden z.B. als transparente Elektroden für EL (Elektrolumineszenz)-Anzeigevorrichtungen sowie Flüssigkristall-Anzeigevorrichtungen, als Elektrodenfilme für Solarzellen und alle Arten von Licht empfangenden Elementen verwendet. Herkömmliche transparente, elektrisch leitende Dünnfilme bestehen z.B. aus Au, SnO2, In2O3,CaO, ZnS oder ZnO. Die meisten dieser Filme haben jedoch den Nachteil einer unzureichenden elektrischen Leitfähigkeit und schlechter mechanischer Eigenschaften (Härte, Schließkontakt) und chemischer Stabilität, so daß derzeit nur In2O3, SnO2 und ITO (Indium-Zinn-Oxid) in größerem Umfang verwendet werden.Transparent, electrically conductive films have high electrical conductivity and transparency in the visible range and are used, for example, as transparent electrodes for EL (electroluminescence) display devices and liquid crystal display devices, as electrode films for solar cells and all types of light-receiving elements. Conventional transparent, electrically conductive thin films consist, for example, of Au, SnO 2 , In 2 O 3 , CaO, ZnS or ZnO. Most of these films, however, have the disadvantage of insufficient electrical conductivity and poor mechanical properties (hardness, make contact) and chemical stability, so that currently only In 2 O 3 , SnO 2 and ITO (indium tin oxide) are used to a greater extent .
Selbst In2O3, SnO2 und ITO weisen jedoch die folgenden Nachteile auf und sind deshalb verbesserungswürdig:Even In 2 O 3 , SnO 2 and ITO, however, have the following disadvantages and are therefore in need of improvement:
- 1. Die thermische Stabilität ist schlecht. Bei der Verwendung in EL-Vorrichtungen erhöht sich der Widerstand bei Wärmeeinwirkung und das In und Sn diffundieren in die Lumineszenzschicht, wodurch der Betrieb der EL-Vorrichtungen beeinträchtigt wird;1. The thermal stability is poor. In the Use in EL devices increases the Resistance to heat and the In and Sn diffuse into the luminescent layer, causing the Operation of the EL devices is impaired;
- 2. Um den Widerstand zu senken, ist während oder nach dem Abscheiden des Films eine Wärmebehandlung bei einer Temperatur über 300°C erforderlich;2. To reduce resistance is during or after Depositing the film at a heat treatment Temperature above 300 ° C required;
- 3. Die Materialien sind extrem kostspielig.3. The materials are extremely expensive.
Im Vergleich zu In2O3 und SnO2 sind die Kosten für Zinkoxid (ZnO) sehr niedrig, so daß es aus wirtschaftlicher Sicht für transparente, elektrisch leitende Filme attraktiv ist. Allerdings ist seine elektrische Leitfähigkeit ungenügend, obwohl seine Transparenz im sichtbaren Bereich recht hoch ist.Compared to In 2 O 3 and SnO 2 , the costs for zinc oxide (ZnO) are very low, so that it is economically attractive for transparent, electrically conductive films. However, its electrical conductivity is insufficient, although its transparency in the visible range is quite high.
Ziel der Erfindung ist es daher, einen transparenten, elektrisch leitenden Film bereitzustellen, der aus einem billigen, hitzebeständigen Material mit hoher elektrischer Leitfähigkeit hergestellt werden kann.The aim of the invention is therefore to provide a transparent, to provide electrically conductive film consisting of a cheap, heat-resistant material with high electrical Conductivity can be established.
Gegenstand der Erfindung ist ein transparenter, elektrisch leitender Film, der in der C-Achse orientiert ist und als Hauptkomponenten Zinkoxid und Aluminium enthält.The invention relates to a transparent, electrical conductive film that is oriented in the C axis and as Main components contain zinc oxide and aluminum.
Der erfindungsgemäße Film wird vorzugsweise durch Gleichstrom- Magnetron-Sputtern unter Verwendung eines Targets abgeschieden, das Zinkoxid als Hauptkomponente, vermischt mit Aluminiumoxid enthält.The film according to the invention is preferably Magnetron sputtering using a target deposited, the zinc oxide as the main component, mixed with aluminum oxide.
In der Zeichnung zeigen:The drawing shows:
Fig. 1 ein Diagramm der Beziehung zwischen der dem Target zugesetzten Aluminiummenge und dem spezifischen Widerstand (p) eines unter Verwendung des Targets hergestellten transparenten, elektrisch leitenden Films; Fig. 1 is a graph showing the relationship between the (p) of a transparent prepared by using the target of the target added amount of aluminum and the specific resistance, the electrically conductive film;
Fig. 2 ein Diagramm der Beziehung zwischen ΔR₅₀ und dem spezifischen Widerstand des transparenten, elektrisch leitenden Films; Fig. 2 is a graph showing the relationship between ΔR ₅₀ and resistivity of the transparent electrically conductive film;
Fig. 3 ein schematisches Diagramm des Aufbaus einer Gleichstrom-Magnetron-Sputtervorrichtung; Fig. 3 is a schematic diagram showing the construction of a DC magnetron sputtering apparatus;
Fig. 4 ein Diagramm der Beziehung zwischen der Substrattemperatur und dem spezifischen Widerstand (p) des transparenten, elektrisch leitenden Films; Fig. 4 is a graph showing the relationship between the substrate temperature and the resistivity (p) of the transparent electroconductive film;
Fig. 5 ein Diagramm der Beziehung zwischen dem Argon- Gasdruck (p Ar ) und dem spezifischen Widerstand (p) des transparenten, elektrisch leitenden Films; Fig. 5 is a graph showing the relationship between the argon gas pressure (p Ar ) and the resistivity (p) of the transparent electroconductive film;
Fig. 6 und 7 Diagramme, aus denen die Abhängigkeit der Filmdicke eines mit Al dotierten ZnO-Films von dem spezifischen Widerstand (p), der Trägerkonzentration (n) und der Hall-Beweglichkeit (µH) bei einem wassergekühlten Substrat (bis zu 100°C) (Fig. 6) bzw. bei einer Substrattemperatur von 300°C (Fig. 7. hervorgeht; FIGS. 6 and 7 are diagrams of which the dependence of the film thickness of an Al-doped ZnO film of the resistivity (p) of the carrier concentration (n) and the Hall mobility (.mu.H) in a water-cooled substrate (up to 100 ° C) ( Fig. 6) or at a substrate temperature of 300 ° C (Fig. 7);
Fig. 8 und 9 die Röntgenbeugungsspektren bei einem wassergekühlten Substrat (bis zu 100°C) (Fig. 8) bzw. einem Substrat von 300°C (Fig. 9). Fig. 8 and 9, the X-ray diffraction spectra at a water-cooled substrate (up to 100 ° C) (Fig. 8) or a substrate of 300 ° C (Fig. 9).
Zinkoxid hat von Haus aus hohe elektrische Leitfähigkeit und auch hohe Transparenz im sichtbaren Bereich. Überraschenderweise wurde nun gefunden, daß der spezifische Widerstand von ZnO durch Zusatz von Aluminium noch weiter gesenkt werden kann und daß ein transparenter, elektrisch leitender Film aus mit Al dotiertem ZnO von überlegener thermischer Stabilität herstellbar ist.Zinc oxide has inherently high electrical conductivity and also high transparency in the visible area. Surprisingly, it has now been found that the specific Resistance of ZnO by adding aluminum even further can be lowered and that a transparent, electric conductive film made of Al doped ZnO of superior thermal stability can be produced.
In Fig. 1 ist die Beziehung zwischen der Zusatzmenge an Aluminium und dem spezifischen Widerstand des transparenten, elektrisch leitenden Films graphisch dargestellt. Die hierbei verwendeten Proben wurden folgendermaßen hergestellt: Eine Mischung aus Al2O3-Pulver und ZnO-Pulver wird gesintert, um ein Target-Material herzustellen. Unter Verwendung dieses Targets werden durch Gleichstrom-Magnetron-Sputtern bei einer Substrattemperatur von 300°C Filmproben mit einer Dicke von 2000 Å hergestellt. Aus Fig. 1 ist ersichtlich, daß sich der spezifische Widerstand mit der Zusatzmenge an Al2O3 ändert.In Fig. 1, the relationship between the amount of aluminum added and the resistivity of the transparent electrically conductive film is graphically shown. The samples used here were produced as follows: A mixture of Al 2 O 3 powder and ZnO powder is sintered to produce a target material. Using this target, film samples with a thickness of 2000 Å are produced by DC magnetron sputtering at a substrate temperature of 300 ° C. From Fig. 1 it can be seen that the specific resistance changes with the amount of Al 2 O 3 added .
Fig. 2 zeigt die Beziehung zwischen (1)Δ R₅₀, d.h. der Halbwertbreite der Rocking-Kurve einer (002)-Ebene als Charakteristikum der C-Achsenorientierung des transparenten, elektrisch leitenden Films, und (2) dem spezifischen Widerstand (p) des Films. Aus der Figur geht hervor, daß mit kleiner werdendem ΔR₅₀ des transparenten, elektrisch leitenden Films, d.h. mit zunehmender C-Achsenorientierung, der spezifische Widerstand (p) abnimmt. Dementsprechend ist es bevorzugt, daß der ΔR₅₀-Wert des transparenten, elektrisch leitenden Films 8,0° oder weniger, insbesondere 4,0° oder weniger, beträgt. Fig. 2 shows the relationship between (1) Δ R ₅₀, the half width of the rocking curve that is a (002) plane as a characteristic of the C-axis orientation of the transparent, electrically conductive film, and (2) the specific resistance (p) of the film. From the figure it can be seen that as the ΔR ₅₀ of the transparent, electrically conductive film becomes smaller, ie with increasing C-axis orientation, the specific resistance (p) decreases. Accordingly, it is preferable that the ΔR ₅₀ value of the transparent electroconductive film is 8.0 ° or less, especially 4.0 ° or less.
Der in der C-Achse orientierte Film aus mit Aluminium dotiertem ZnO kann auf einem geeigneten Substrat hergestellt werden, z.B. nach einem Sputter-Verfahren wie dem Gleichstrom-Magnetron-Sputtern oder RF-Magnetron-Sputtern, durch Aufdampfen oder Ionenplattieren. Unter diesen Methoden ist das Gleichstrom-Magnetron-Sputtern besonders bevorzugt. Aus diesem Grund wird im folgenden die Herstellung eines transparenten, elektrisch leitenden Films durch Gleichstrom-Magnetron-Sputtern näher erläutert.The film made with aluminum in the C-axis doped ZnO can be produced on a suitable substrate e.g. after a sputtering process like that DC magnetron sputtering or RF magnetron sputtering, by vapor deposition or ion plating. Under these Methods, DC magnetron sputtering is special prefers. For this reason, the following is the Production of a transparent, electrically conductive film explained in more detail by direct current magnetron sputtering.
Fig. 3 zeigt schematisch den Aufbau einer Gleichstrom- Magnetron-Sputtervorrichtung. In einer Vakuumkammer (11) ist eine Sputter-Elektrode (13) vorgesehen. Auf der Oberseite der Sputter-Elektrode (13) befindet sich ein Target (15). Gegenüber dem Target (15) wird in einer Position parallel zur Oberfläche des Targets (15) ein Substrat (17) gehalten. In der Vakuumkammer (11) wird mit Hilfe eines Vakuumsystems (21) ein Hochvakuum von z.B. 10-6 bis 10-7 Torr erzeugt, worauf man ein Sputter-Gas, wie Ar oder Ar + O2, durch ein Gaseinlaßventil (23) einleitet, bis das Vakuum 10-2 bis 10-3 Torr beträgt, um den Sputter- Druck einzustellen. Anschließend legt man an die Elektroden mit Hilfe einer Sputter-Spannungsquelle (25) eine Hochspannung an, wobei aus dem Magnetfeld eines (nicht gezeigten Magneten), der an der Rückseite der Sputter- Elektrode (13) angeordnet ist, eine Magnetronentladung erfolgt und das Target (15) gesputtert wird, so daß auf dem Substrat (17) ein transparenter, elektrisch leitender Film entsteht. In Fig. 3 wird eine Gleichspannungsquelle als Spannungsquelle (25) verwendet, jedoch kann in einem RF- Magnetron-Sputterverfahren auch eine RF-Energiequelle eingesetzt werden. Im Gleichstrom-Magnetron-Sputterverfahren ist die Sputter-Geschwindigkeit hoch und es kommt praktisch zu keiner Hitzeschädigung der Substratoberfläche. In der Figur wird zur Messung der Substrattemperatur ein Thermoelement (19) angewandt. Fig. 3 shows schematically the structure of a direct current magnetron sputtering device. A sputter electrode ( 13 ) is provided in a vacuum chamber ( 11 ). A target ( 15 ) is located on the top of the sputter electrode ( 13 ). A substrate ( 17 ) is held in a position parallel to the surface of the target ( 15 ) opposite the target ( 15 ). In the vacuum chamber (11) of a vacuum system (21) is a high vacuum of for example 10 with the aid - from 6 to 10 - 7 generates Torr, after which a sputtering gas such as Ar or Ar + O 2, initiates through a gas inlet valve (23) until the vacuum 10-2 to 10-3 Torr, in order to adjust the sputtering pressure. A high voltage is then applied to the electrodes with the aid of a sputter voltage source ( 25 ), a magnetron discharge and the target taking place from the magnetic field of a magnet (not shown) which is arranged on the rear of the sputter electrode ( 13 ) ( 15 ) is sputtered, so that a transparent, electrically conductive film is formed on the substrate ( 17 ). In Fig. 3, a DC voltage source is used as the voltage source ( 25 ), but an RF energy source can also be used in an RF magnetron sputtering method. In the direct current magnetron sputtering process, the sputtering speed is high and there is practically no heat damage to the substrate surface. In the figure, a thermocouple ( 19 ) is used to measure the substrate temperature.
Vorzugsweise liegt die Zusammensetzung des Targets im Bereich von 0,5 bis 5 Gewichtsprozent, insbesondere 1,0 bis 4,0 Gewichtsprozent, bezogen auf (Al2O3)/(ZnO + Al2O3).The composition of the target is preferably in the range from 0.5 to 5 percent by weight, in particular 1.0 to 4.0 percent by weight, based on (Al 2 O 3 ) / (ZnO + Al 2 O 3 ).
Das Target kann z.B. dadurch hergestellt werden, daß man ZnO-Pulver und Al2O3-Pulver miteinander vermischt, die Mischung bei etwa 800°C vorsintert, dann pulverisiert und komprimiert, worauf man eine volle Sinterung des komprimierten Gemisches bei etwa 900 bis 1000°C durchführt und das gesinterte Gemisch einer Wärmebehandlung bei hohen Temperaturen, z.B. etwa 1300°C, unterwirft, um den spezifischen Widerstand zu senken.The target can be produced, for example, by mixing ZnO powder and Al 2 O 3 powder with one another, pre-sintering the mixture at about 800 ° C., then pulverizing and compressing, followed by full sintering of the compressed mixture at about 900 to 1000 ° C and the sintered mixture is subjected to a heat treatment at high temperatures, for example about 1300 ° C, in order to reduce the specific resistance.
In Fig. 4 ist die Beziehung zwischen der Substrattemperatur und dem spezifischen Widerstand (p) des transparenten, elektrisch leitenden Films graphisch dargestellt. Es ist ersichtlich, daß der Widerstand (p) abnimmt, wenn sich die Substrattemperatur erhöht. Das Widerstandsminimum beträgt 2 bis 3 × 10-4 Ohm cm, wenn die Substrattemperatur beträgt, und wenn die Substrattemperatur 300°C überschreitet, steigt der Widerstand (p) wieder beträchtlich an. Diese Analyse wird unter Anwendung der Gleichstrom-Magnetron- Sputtermethode bei einem Argon-Gasdruck von 0,5×102 Torr und einer Filmdicke von 2000 Å durchgeführt. Erfindungsgemäß ist es somit möglich, einen transparenten, elektrisch leitenden Film mit kleinem spezifischem Widerstand bei relativ niedriger Temperatur herzustellen. Fig. 4 graphically shows the relationship between the substrate temperature and the resistivity (p) of the transparent electrically conductive film. It can be seen that the resistance (p) decreases as the substrate temperature increases. The resistance minimum is 2 to 3 × 10 -4 ohm cm when the substrate temperature is, and when the substrate temperature exceeds 300 ° C, the resistance (p) increases considerably again. This analysis is carried out using the DC magnetron sputtering method at an argon gas pressure of 0.5 × 10 2 Torr and a film thickness of 2000 Å. According to the invention, it is thus possible to produce a transparent, electrically conductive film with a low specific resistance at a relatively low temperature.
Fig. 5 zeigt die Beziehung zwischen dem Argon-Gasdruck (P Ar ) und dem Widerstand (p) im Falle der Herstellung des transparenten, elektrisch leitenden Films bei einer Substrattemperatur von 300°C und einer Filmdicke von 2000 Å nach dem Magnetron-Sputterverfahren. Je niedriger der Argon-Gasdruck ist, desto niedriger ist der spezifische Widerstand des erhaltenen elektrisch leitenden Films. Fig. 5 shows the relationship between the argon gas pressure (P Ar ) and the resistance (p) in the case of producing the transparent, electrically conductive film at a substrate temperature of 300 ° C and a film thickness of 2000 Å by the magnetron sputtering method. The lower the argon gas pressure, the lower the specific resistance of the electroconductive film obtained.
Fig. 6 und 7 zeigen die Abhängikeit der Filmdicke eines mit Al dotierten ZnO-Films in Bezug auf den spezifischen Widerstand (p), die Trägerkonzentration (n) und die Hall- Mobilität (µH) bei einem wassergekühlten Substrat (bis zu 100°C) (Fig. 6) bzw. bei einer Substrattemperatur von 300°C (Fig. 7). Bei der Substrattemperatur von 300°C ist der Widerstand kleiner, während n und µH größer sind, und die Filmdicken-Abhängigkeit ist stärker verbessert im Vergleich zu dem wassergekühlten Substrat. FIGS. 6 and 7, the Abhängikeit show the film thickness of a doped Al ZnO film in terms of the resistivity (p), the carrier concentration (n) and the Hall mobility (.mu.H) in a water-cooled substrate (up to 100 ° C ) ( Fig. 6) or at a substrate temperature of 300 ° C ( Fig. 7). At the substrate temperature of 300 ° C, the resistance is smaller, while n and µH are larger, and the film thickness dependency is more improved compared to the water-cooled substrate.
Fig. 8 und 9 zeigen Röntgenbeugungsspektren bei einem wassergekühlten Substrat (Fig. 8) bzw. bei einer Substrattemperatur von 300°C (Fig. 9). In beiden Fällen werden Peaks nur in den (002)- und (004)-Ebenen beobachtet und die Filmstruktur ist in der C-Achse orientiert. Die Beugungsstärke ist etwa zwanzig Mal größer bei einer Substrattemperatur von 300°C im Vergleich zu dem wassergekühlten Substrat, so daß für dieses Material eine stärkere C-Achsenorientierung anzunehmen ist. Außerdem weist der durch Gleichstrom-Magnetron-Sputtern hergestellte, mit Al dotierte ZnO-Film eine Durchlässigkeit von mehr als 80% im sichtbaren Bereich auf. FIGS. 8 and 9 show X-ray diffraction spectra at a water-cooled substrate (Fig. 8) or at a substrate temperature of 300 ° C (Fig. 9). In both cases, peaks are only observed in the (002) and (004) planes and the film structure is oriented in the C axis. The diffraction strength is about twenty times greater at a substrate temperature of 300 ° C compared to the water-cooled substrate, so that a stronger C-axis orientation can be assumed for this material. In addition, the Al-doped ZnO film produced by direct current magnetron sputtering has a permeability of more than 80% in the visible range.
Die folgenden Beispiele erläutern die Erfindung. The following examples illustrate the invention.
ZnO-Pulver und Al2O3-Pulver werden derart miteinander vermischt, daß das Verhältnis (Al2O3)/(ZnO + Al2O3) 2,0 Gewichtsprozent beträgt. Nach dem Vorsintern bei etwa 800°C wird pulverisiert und komprimiert, worauf man das Gemisch bei 900 bis 1000°C sintert und einer Wärmebehandlung bei 1300°C unterzieht. Es wird ein Target-Material mit geringem spezifischem Widerstand erhalten.ZnO powder and Al 2 O 3 powder are mixed together in such a way that the ratio (Al 2 O 3 ) / (ZnO + Al 2 O 3 ) is 2.0 percent by weight. After presintering at about 800 ° C., the mixture is pulverized and compressed, whereupon the mixture is sintered at 900 to 1000 ° C. and subjected to a heat treatment at 1300 ° C. A target material with low resistivity is obtained.
Unter Verwendung dieses Targets wird mit der Vorrichtung von Fig. 3 ein erfindungsgemäßer transparenter, elektrisch leitender Film Nr. 1 auf eine 7059-Glasplatte von der Corning Co. bei einer Substrattemperatur von 300°C durch Gleichstrom-Magnetron-Sputtern hergestellt.Using this target, the device of FIG. 3 is used to produce a transparent, electrically conductive film No. 1 according to the invention on a 7059 glass plate from Corning Co. at a substrate temperature of 300 ° C. by direct current magnetron sputtering.
Die Eigenschaften des erhaltenen transparenten, elektrisch leitenden Films sind in Tabelle 1 genannt zusammen mit den Eigenschaften anderer Beispiele von erfindungsgemäßen transparenten, elektrisch leitenden Filmen.The properties of the obtained transparent, electrical conductive films are listed in Table 1 along with the Properties of other examples of the invention transparent, electrically conductive films.
Beispiel 1 wird wiederholt, jedoch hält man die Substrattemperatur durch Kühlen mit Wasser bei 100°C oder weniger. Es wird ein erfindungsgemäßer transparenter, elektrisch leitender Film Nr. 2 erhalten.Example 1 is repeated, but you keep the Substrate temperature by cooling with water at 100 ° C or fewer. A transparent, obtained electroconductive film No. 2.
Ein transparenter, elektrisch leitender Film wird auf der Glasplatte von Beispiel 1 bei einer Substrattemperatur von 300°C mit einem Verhältnis (Al2O3)/(ZnO + Al2O3) von 2,0 Gewichtsprozent hergestellt, wobei man eine gleichzeitige Ionenplattierung von Al2O3 und ZnO aus getrennten Verdampfungsquellen durchführt. Es wird ein erfindungsgemäßer transparenter, elektrisch leitender Film Nr. 3 erhalten.A transparent, electrically conductive film is produced on the glass plate of Example 1 at a substrate temperature of 300 ° C. with a ratio (Al 2 O 3 ) / (ZnO + Al 2 O 3 ) of 2.0 percent by weight, with simultaneous ion plating of Al 2 O 3 and ZnO from separate evaporation sources. A transparent, electrically conductive film No. 3 is obtained.
Beispiel 1 wird wiederholt, jedoch verwendet man als Substrat eine Polyethylenterephthalatfolie anstelle der Glasplatte und hält die Substrattemperatur durch Kühlen mit Wasser bei 100°C oder weniger. Es wird ein erfindungsgemäßer transparenter, elektrisch leitender Film Nr. 4 erhalten.Example 1 is repeated, but is used as A polyethylene terephthalate film instead of the substrate Glass plate and keeps the substrate temperature by cooling Water at 100 ° C or less. It becomes an inventive one Obtain transparent, electrically conductive film No. 4.
Erfindungsgemäß wird ein transparenter, elektrisch leitender Film mit guter thermischer Beständigkeit und Stabilität sowie niedrigem spezifischen Widerstand erhalten. Selbst bei Temperaturen unter 100°C kann ein transparenter, elektrisch leitender Film mit niedrigem Widerstand in der Größenordnung von 10-3 bis 10-4 Ohm · cm hergestellt werden. Da ferner keine Wärmebehandlung nach der Filmbildung erforderlich ist, können transparente, elektrisch leitende Filme auf Kunststoffolien mit geringer Wärmebeständigkeit ausgebildet werden. Ein zusätzlicher Vorteil ist darin zu sehen, daß das erfindungsgemäß angewandte ZnO und Al2O3 im Vergleich zu In2O3 und SnO2 einen sehr niedrigen Preis haben.According to the invention, a transparent, electrically conductive film with good thermal resistance and stability and low specific resistance is obtained. Even at temperatures below 100 ° C, a transparent, electrically conductive film with low resistance in the order of 10 - 3 to 10 - 4 Ohm · cm can be produced. Furthermore, since no heat treatment is required after film formation, transparent, electrically conductive films can be formed on plastic films with low heat resistance. An additional advantage can be seen in the fact that the ZnO and Al 2 O 3 used according to the invention have a very low price compared to In 2 O 3 and SnO 2 .
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JP60262940A JPH0731950B2 (en) | 1985-11-22 | 1985-11-22 | Method for producing transparent conductive film |
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DE19863639508 Ceased DE3639508A1 (en) | 1985-11-22 | 1986-11-20 | Transparent, electrically conducting film and method of fabricating it |
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EP0229509A2 (en) * | 1985-12-18 | 1987-07-22 | CPFilms, Inc. | Stable high resistance transparent coating |
EP0229509A3 (en) * | 1985-12-18 | 1989-11-29 | CPFilms, Inc. | Stable high resistance transparent coating |
US4948529A (en) * | 1985-12-18 | 1990-08-14 | Andus Corporation | Stable high resistance transparent coating |
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EP0354769A3 (en) * | 1988-08-09 | 1991-11-21 | Tosoh Corporation | Zinc oxide sintered body and preparation process thereof |
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EP0486182A1 (en) * | 1990-11-15 | 1992-05-20 | Tosoh Corporation | Zinc oxide sintered body, and production and application thereof |
US5171411A (en) * | 1991-05-21 | 1992-12-15 | The Boc Group, Inc. | Rotating cylindrical magnetron structure with self supporting zinc alloy target |
DE29711973U1 (en) * | 1997-07-08 | 1998-11-05 | Glas Platz Fa | Electrical device, electrical device or lighting device |
DE10306925A1 (en) * | 2003-02-19 | 2004-09-02 | GfE Gesellschaft für Elektrometallurgie mbH | PVD coating material |
WO2004075212A1 (en) * | 2003-02-19 | 2004-09-02 | GfE Gesellschaft für Elektrometallurgie mbH | Pvd coating material |
US7867636B2 (en) | 2006-01-11 | 2011-01-11 | Murata Manufacturing Co., Ltd. | Transparent conductive film and method for manufacturing the same |
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DE102007024986A1 (en) | 2007-05-28 | 2008-12-04 | Forschungszentrum Jülich GmbH | Temperature-stable TCO layer, method of manufacture and application |
EP2028695A1 (en) * | 2007-07-12 | 2009-02-25 | Applied Materials, Inc. | Method for creating a transparent conductible oxide coating |
EP2166132A2 (en) * | 2008-05-13 | 2010-03-24 | Nitto Denko Corporation | Transparent conductive film and method for production thereof |
EP2166132A3 (en) * | 2008-05-13 | 2010-03-31 | Nitto Denko Corporation | Transparent conductive film and method for production thereof |
CN103046013A (en) * | 2012-12-30 | 2013-04-17 | 青海天誉汇新能源开发有限公司 | Method for preparing photovoltaic cell transparent oxide film with flexible substrate |
Also Published As
Publication number | Publication date |
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JPH0731950B2 (en) | 1995-04-10 |
JPS62122011A (en) | 1987-06-03 |
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