EP1282919A1

EP1282919A1 - Indium-tin-oxide (ito) layer and method for producing the same

Info

Publication number: EP1282919A1
Application number: EP01933932A
Authority: EP
Inventors: Andreas KLÖPPEL; Jutta Trube
Original assignee: Unaxis Deutschland Holding GmbH
Current assignee: Oerlikon Deutschland Holding GmbH
Priority date: 2000-05-12
Filing date: 2001-05-04
Publication date: 2003-02-12
Also published as: US6849165B2; US7285342B2; DE10023459A1; JP2003532997A; US20050175862A1; US20030170449A1; KR20030024665A; TWI253477B; JP5144868B2; WO2001086731A1; KR100821353B1

Abstract

The invention relates to a method for precipitating transparent and conductive indium-tin-oxide (ITO) layers, which have a particularly low resistance of preferably less than 200 νΦcm and a low degree of surface roughness of preferably less than 1 nm, onto a substrate. To this end, a combined HF/DC sputtering of an indium-tin-oxide (ITO) target is used in which an Ar/H2 mixture serving as a reaction gas is fed to the process gas during sputtering. The invention also relates to (ITO) layers having the aforementioned properties.

Description

Indium tin oxide (ITO) layer and method of manufacturing the same

The present invention relates to an indium tin oxide (ITO) layer for nerve use as a transparent, conductive electrode, in particular in organic LED displays, and to a method for the deposition of transparent and conductive indium tin oxide (ITO) layers a substrate.

For flat monitors and screens, such as are used for example in portable computers or in displays for mobile phones, such as. B. liquid crystal displays, organic LED displays, TFT screens, etc. transparent and conductive electrode layers are required. Indium-tin-oxide layers (ITO layers) are usually used for this, which best meet the requirements with regard to conductivity and transmission properties. These ITO layers are usually applied to transparent substrate material, such as in particular glass, transparent plastics, combined glass / plastic laminates, etc., by sputter deposition (sputtering) of an ITO target.

For example, Ishibashi et al. in "Low Resistivity Indium-Tin Oxide Transparent Conductive Films, I. Effect Of Introducing HO Gas or H -Gas During Direct Current Magnetron Sputtering", J Nac. Sei. Technol. A 8 (3) May / June 1990, a direct current ( DC) - Magnetron sputter ner driving, in which by adding water vapor or hydrogen to the process gas an ITO layer can be deposited at a deposition temperature of less than 200 ° C, which has a specific resistance of approx. 6 x 10 ^"4 Ωcm , The low deposition temperature or substrate temperature of below 200 ° C. is important in this context, because at a higher deposition or substrate temperature, the sputtering process leads to the desired results more easily, but both the deposited layer and that Substrate could be damaged. This is particularly for substrates such as. B. plastic substrates such. B. polyethylene terephthalate (PET) important, which would be destroyed at higher temperatures.

Another method for the deposition of ITO layers with low resistance is described by BH Lee et al. in "Effect Of Base Pressure in Sputter Deposition On Characteristics of Indium Tin Oxide Thin Film", Fiat panel display Materials II, Sypmposium San Franciso, CA, USA, April 8-12, 1996, Mat.Res. Soc.Symp Proc.Nol.424, 1997. This method is a combined radio frequency (RF) and DC magnetron sputtering method in which an ITO target is used with the same proportions of DC sputterers and RF sputterers atomized and a layer with a specific resistance of less than 1.5x10 ^" Ωcm. Argon was used as the process gas.

However, although the layers produced by the above methods have a low specific resistance, they have the disadvantage that they have a high surface roughness. In particular, the surface structure of such ITO layers is characterized by a domain structure with grains of different crystal orientation within the domains, with individual grains having peaks protruding from the surface (so-called spikes). The rough surface and the so-called ITO spikes mean that when the ITO layer is used as an electrode they act as field tips and thus reduce the lifespan of organic LED cells, for example, if such ITO layers as electrodes in organic LED Displays are used. In addition, the increased surface roughness leads to a reduced efficiency of such organic LED cells. Another disadvantage can be seen in the fact that the ITO spikes in the manufacture of organic LED displays can lead to the fact that when the organic materials are deposited on the ITO layer, the tips are not covered with the organic material and then used can then lead to short circuits.

It is therefore an object of the present invention to provide ITO layers and a method for depositing ITO layers, in which ITO layers can be produced which have a low surface roughness, preferably below 1 nm, and a low specific resistance, preferably have less than 200 μΩcm, the deposition temperature or temperature of the substrate on which the ITO layers are to be deposited should be low, in particular below 250 ° C., preferably below 200 ° C. In particular, in the case of an industrially usable process or corresponding ITO layers, i. i.e., taking into account a simple and inexpensive implementation, in particular the so-called ITO spikes can be avoided.

This object is achieved with the method according to claim 1 and the ITO layer according to claim 7. Advantageous refinements are the subject of the subclaims.

The inventive method for the deposition of transparent and conductive indium tin oxide (ITO) layers, in which the layers in particular have a low specific resistance and a very smooth surface, comprises a combined high frequency / direct current (HF / DC) sputtering Process in an atmosphere which has an argon-hydrogen mixture as the reaction gas. By using an RF As part of the power in the high-frequency range for sputtering known to the person skilled in the art, a reactive gas activation is achieved in the HF plasma for the selected reactive gas mixture argon / hydrogen, which has a positive effect on the properties of the deposited ITO layer. In particular, the surface roughness and the specific resistance of the layer are significantly reduced, the substrate temperature being able to be kept at a low value of less than 250 ° C., preferably ≤ 200 ° C. Due to the lower surface roughness, when using such deposited ITO layers for organic LED cells, greater efficiency, greater yield and longer service life can be achieved for organic LED displays. In addition, the reduction in the specific resistance means that, for certain applications with a fixed sheet resistance for the ITO layer, a smaller necessary layer thickness can be selected, so that a lower material requirement for indium tin oxide is required.

Known ITO targets are used for sputtering, which preferably comprise 90% In O ₃ and 10% SnO ₂ . The HF power component of the total power during sputtering is preferably set to at least 30%, in particular 60% and more, preferred ranges being in the range from 40 to 90% HF power component, in particular 60 to 80% HF power components.

The Ar / H mixture added to the process gas according to the invention is preferably in a mixing ratio of 80% argon and 20% hydrogen. Such an Ar / H ₂ mixture is advantageously added to a process gas usually made of argon in the order of 0.1-30%, in particular 5-15%, but preferably in the range 8-10%.

The total pressure of the process gas can also play a role in the deposition of the ITO layers. It has been shown here that particularly good results are achieved, in particular in the range of a total pressure of 0.5 to 5 μbar, preferably 1 to 3 μbar and most preferably 1.5 to 2 μbar.

In a preferred embodiment, which is chosen in particular when depositing ITO layers on plastics, the substrate temperature is reduced to a max. 250 ° C, but preferably set to ≤ 200 ° C. This has the advantage that neither the substrate nor the layer itself is damaged by an excessively high temperature. Although the method described is not limited to the use of magnetron sputter systems, it is preferred, however, to use a corresponding magnetron arrangement to undersize the sputter deposition.

The ITO layers according to the invention, which are produced in particular using the method described above, have a smooth surface with a surface roughness of less than 1 nm and have a specific resistance which is below 200 μΩcm, in particular in the range from 140 to 160 μΩcm.

Further advantages, characteristics and features of the invention will become apparent from the following detailed description of preferred exemplary embodiments. The diagrams show in

Fig.l the dependence of the surface roughness (RMS roughness) of ITO

Layers of the RF power component during the deposition with a power density of P = 2 W / cm ² and a substrate temperature of T _sub = 200 ° C;

2 shows the dependence of the specific resistance p of ITO layers on the HF

Power _share in the deposition with a power density of P = 2 W / cm ² and a substrate temperature of T _SUb = 200 ° C; and in

Fig. 3 atomic force microscopic (AFM) recordings in 60,000 times magnification of ITO layers, which were deposited with different HF power _components at a substrate temperature of T _SUb = 200 ° C. only DC sputtering,

33% HF power share in HF / DC sputtering

66% HF power share, only HF sputtering.

1 shows the dependence of the surface roughness on the HF power component in the inventive deposition of ITO layers. With increasing HF power share in the combined HF / DC sputtering, an increasingly smoother surface is achieved. A significant reduction in surface roughness is observed in particular from an HF power component of approx. 30% and more. From an HF power component of approx. 65%, there is a saturation with regard to the influence on the surface roughness.

FIG. 2 shows the dependence of the specific resistance p on ITO layers, which were deposited with an increasing HF power component. It can also be seen here that the specific resistance decreases with increasing HF power share. A particularly significant reduction is observed up to an RF power component of approx. 30%, while from this point only a small, continuous decrease in the specific resistance can be observed with an increasing RF power component.

3 shows the influence of the HF power component in the combined HF / DC sputtering on surfaces of ITO layers which are deposited at a substrate temperature of 200 ° C.

The illustrations shown in FIG. 3 show AFM images of ITO layers with a magnification of 60,000 times, which can only be obtained by DC sputtering (a), with combined HF / DC sputtering with an HF power share of 33% (b). , with an RF power share of 66% (c) and have been separated using only HF sputtering. The AFM images clearly show that a significantly smoother surface structure can be achieved with an increasing HF power component, an optimum in terms of surface roughness being found in particular with an HF power component of 66%.

According to the invention, in a preferred exemplary embodiment, an ITO layer was deposited on float glass with the following parameters:

Target: ITO Mitsui (90% In ₂ 0 ₃ /10% SnO ₂ )

Purity: 4N, density> 98%

Total sputtering power: 860 W (570 W HF / 290 W DC)

HF power share: 66%

Process pressure: 1.5 μbar, Ar / H ₂ content (80% / 20% mixture): 8%

Deposition temperature: 200 ° C

Magnetic field strength: 1200 G.

Substrate: float glass

Layer thickness: 72 nm

In the case of an ITO layer which was deposited by magnetron sputtering using the above process parameters, an RMS roughness of 0.623 nm was determined using AFM (probe force microscope). The RMS roughness (root mean square roughness) is defined as the standard deviation of the Z values (height range), which were determined during the measurement with the atomic force microscope. The specific resistance of the layer was 152 μΩcm. The transmission at 550 nm wavelength was 81% compared to the reference air. These results show that the method described above can be used to produce layers according to the invention which, in particular with regard to surface roughness and specific resistance, have excellent properties for use in organic LED displays.

Claims

claims

1. A method for the deposition of transparent and conductive indium tin oxide (ITO) layers with in particular a low resistance of preferably below 200 μΩcm and a low surface roughness of preferably less than 1 nm on a substrate, characterized by combined HF / DC sputtering Indium-tin-oxide (ITO) targets, whereby an Ar / ΕL mixture is added as the reaction gas to the process gas during sputtering.

2. The method according to claim 1, characterized in that the HF power share of the total power during sputtering is at least 30%, preferably 60% and more, in particular 40% to 90%, preferably 60 to 80%.

3. The method according to any one of the preceding claims, characterized in that the mixing ratio of the Ar / H ₂ mixture is 80:20 and the proportion of the Ar / H ₂ mixture in the process gas 0.1 to 30%, in particular 5 to 15% , preferably 8 to 10%.

4. The method according to any one of the preceding claims, characterized in that the pressure of the process gas during sputtering is 0.5 to 5 μbar, preferably 1 to 3 μbar, in particular 1.5 to 3 μbar.

5. The method according to any one of the preceding claims, characterized in that magnetron sputtering is used for sputtering.

6. The method according to any one of the preceding claims, characterized gekennzeiclinet that the substrate temperature during the deposition of the ITO layer does not exceed 250 ° C, preferably 200 ° C.

7. indium tin oxide (ITO) layer for use as a transparent, conductive electrode, in particular in organic LED displays, on a substrate, in particular produced by the method according to any one of the preceding claims, characterized in that the layer has a specific Resistance of less than 200 μΩcm and a surface roughness of less than 1 nm.

8. ITO layer according to claim 7, characterized in that the specific resistance is 120 to 180 μΩcm.