PROCESS FOR PRODUCING TRANSPARENT CONDUCTIVE FILM COATED WITH METAL OXIDE THIN FILM

Abstract: A transparent conductive film coated with a metal oxide thin film which has a uniform light trans­ mittance, a uniform sheet resistance and a uniform adhesion can be semi-continuously produced by (a) using a semi-continuous roll to roll sputtering apparatus for a substrate film which comprises a plasma emission spectroanalysis system, a system for measuring the light transmittance and sheet resistance of the resulting film and a system for feeding the measurement results of the above two systems to a controller for the rate of oxygen fed or the discharge current or power, (b) measuring the light transmittance and sheet resistance of the film produced as well as the atomic spectral intensities of the target component and argon present in the vicinity of the target surface, and (c) controlling the rate of oxygen fed or the discharge power or current so that the measure­ ment data of the atomic spectral intensities of the target component and argon or their computation results may be kept constant and further simultaneously controlling the anode current so that the atomic spectral intensity of argon may be kept in a given range, in order to keep the light transmittance and sheet resistance of the resultant film in the respective predetermined ranges and to keep a good adhesion between the substrate film and the thin film.

Description: The present invention relates to a process for producing a transparent conductive film coated with a metal oxide thin film which has a uniform light transmittance, a uniform sheet resistance and a uniform adhesion. The conventional process for producing a film coated with a metal oxide thin film, using an apparatus which enables semi-continuous roll to roll metal oxide deposition on a ribbon-shaped film by reactive sputtering is characterized by being able to easily obtain a film having a metal oxide thin film of large area and accordingly is industrially very effective. In the process, however, the surface condition of the target changes with time even when the cathode current, the anode current, the temperature of the film fed, the rate of oxygen fed and the rate of argon fed are kept constant. As a result, there occurs the fluctuation of deposition rate and the oxidation degree of a metal to be adhered to a film, i.e., the fluctuation of the light transmittance, adhesion (adhesion between a substrate film and a metal oxide thin film) and sheet resistance of the film produced. Hence, it becomes necessary to always control the cathode current, the anode current or the rate of oxygen fed in order to made constant the light transmittance, adhesion and sheet resistance of the film produced. However, it has been difficult to always keep, during thin film formation, the rate of oxygen fed or the cathode current and the anode current at the respective optimum levels in order to make constant at a high precision the deposition rate and the oxidation degree of a metal oxide to be adhered to a film and thereby to obtain a continuous ribbon-shaped film having a uniform light transmittance, a uniform sheet resistance and a uniform adhesion. US-A-4 113 599 describes the cathode sputtering technique for the deposition of indium oxide on glass and to obtain consistent properties for the indium oxide layers deposited by this method by adjusting the flow rate of oxygen to maintain a constant discharge current while adjusting the flow rate of argon to maintain a constant pressure in the sputtering chamber. In order to improve the properties of film-material it is required according to the present invention to include the controlling of the light transmittance and the sheet resistance and to process the film and evaluate the data with a new technique. The object of the present invention is to obtain a film coated with a metal oxide thin film which has a uniform light transmittance, a uniform sheet resistance and a uniform adhesion, by the use of a sputtering apparatus of semi-continuous operation type. In order to achieve the above object, the present inventors made research on the automatic control of the rate of oxygen fed in place of the conventional manual control to set the flow of a constant current through a target. As a result, the present inventors found that a transparent conductive film coated with a metal oxide thin film which has a uniform light transmittance, a uniform sheet resistance and a uniform adhesion, can be easily produced by using a method of controlling the rate of oxygen fed or the cathode current or the cathode power so that the measurement data of the atomic spectral intensities of the target component and argon both present in the plasma generated near the target during film formation or their computation results are kept constant and further by controlling the anode current so that the atomic spectral intensity of argon is kept in a given range. Further research was made based on the above finding and the present invention has been completed. The present invention provides a process for semi-continuously producing a transparent conductive film coated with a metal oxide thin film which has a uniform light transmittance, a uniform sheet resistance and a uniform adhesion, which process comprises (a) using a semi-continuous roll-to-roll sputtering apparatus for a substrate film which comprises a plasma emission spectroanalysis system, a system for measuring the light transmittance and sheet resistance of the resulting film and a system for feeding the measurement data of the above two systems to a controller for the rate of oxygen fed or the discharge current or power, (b) measuring the light transmittance and sheet resistance of the film produced as well as the atomic spectral intensities of the target component and argon present in the vicinity of the target surface, and (c) controlling the rate of oxygen fed or the discharge power or current so that the measurement data of the atomic spectral intensities of the target component and argon or their computation results are kept constant and further simultaneously controlling the anode current so that the atomic spectral intensity of argon is kept in a given range, in order to keep the light transmittance and sheet resistance of the resultant film in the respective predetermined ranges. Fig. 1 is a schematic diagram showing an apparatus for semi-continuously producing a transparent conductive film coated with ITO (indium tin oxide) which is used in the present invention. Fig. 2 is a graph showing a relationship between (a) the ratio of the atomic spectral intensity of indium to that of argon and (b) the sheet resistance or light transmittance of the objective film, when the rate of oxygen was changed in the process of the present invention. The meanings of the reference numbers in Fig. 1 are as follows; 1: closed vessel, 2: film, 3: film temperature-controlling drum, 4: anode, 5 target, 5': cathode, 6: massflow controller, 7: O₂ tank, 7' Ar tank, 8: arithmetic unit, 9: anode power source, 10: cathode power source, 11: resistance meter, 12: light transmittance meter, 13: plasma monitor, 13' window, 14: digital computer, 15: feed roll, and 16: wind-up roll. The present invention is a process for semi-continuously forming a metal oxide thin film on a substrate film so that the resulting film may have a uniform light transmittance, a uniform sheet resistance and a uniform adhesion between the substrate film and the metal oxide thin film. Hereinafter the present invention is explained in more detail referring to the accompanying drawings. The present invention is a process for producing a transparent conductive film coated with a metal oxide thin film which has a uniform light transmittance, a uniform sheet resistance and a uniform adhesion, by (a) using a sputtering apparatus comprising a closed vessel (1) having an exhaust system capable of keeping a vacuum of 1.3332 · 10⁻³ - 1.3332 · 10⁻⁵ Pa (10⁻⁵ - 10⁻⁷ Torr), a feed roll (15) for a film (2), a film wind-up roll (16), a roll (3) for controlling the film temperature during thin film formation, a metal plate (the so-called target) (5) which provides a material for the thin film, a magnet for applying a magnetic field to the surface of the target, a cathode power source (10) for sputtering, an anode (4) for promoting the oxidation of the sputtered target component at the time of thin film formation, massflow controllers (6) for feeding oxygen and argon into the closed vessel (1), a plasma monitor (13) for measuring the atomic spectral intensities of argon and indium at the target surface, and a light transmittance meter (12) and a resistance meter (11) both for measuring the properties of the resultant film before winding up, (b) measuring, during the process, the light transmittance and sheet resistance of the resultant film between the film temperature-controlling roll (3) and the wind-up roll (16), as well as the atomic spectral intensities of the target component and argon both at the target surface, and (c) controlling, during the process, the rate of oxygen fed or the cathode current as well as the anode current so that the measurement data of the atomic spectral intensities of the target component and argon or their computation results are kept constant in order to keep the light transmittance and sheet resistance of the resultant film in the respective predetermined ranges. As the substrate film, there are used films of polyether sulfone (PES), polyethylene terephthalate (PET), polyimide (PI), polyether imide (PEI), polycarbonate (PC), and the like. As the target component, there can be cited In, Sn, indium-tin alloy, Si, Ti, Ce, Zn, and the like. Typical reactive sputtering is started by the impact of excited and positively ionized argon applied onto the surface of a target; the impact sputters the target component; the sputtered component reacts with oxygen fed together with said argon; and the reaction product deposits on an objective material to be coated. In the course of sputtering, the target is exposed to oxygen and oxidized thereby and, as a result, the surface condition of the target changes with time. Consequently, the rate of deposition and the quality of the thin film formed by deposition changes with time even if the rate of oxygen fed is kept constant. The anode current has a correlation to the energy of argon which impinges on the target surface. Naturally, the anode current greatly affects the energy of the sputtered target component and the residual stress of the component after deposition, i.e., the adhesion of the deposited component to the substrate film, and therefore it is preferable that the anode current be kept low. However, as the anode current is lowered, the light transmittance of the resulting film decreases and the sheet resistance of the film increases. Hence, it becomes necessary to control the rate of oxygen fed and the anode current. Plasma is generated in the thin film formation process by sputtering. The atomic spectral intensities of the target component and argon present in the plasma correspond to the respective amounts present in the plasma. The proportion of the amount of the target component to the amount of argon idicates the surface condition of the target. For example, the introduction of oxygen at a large amount increases the oxidation of the target surface and reduces the sputtering rate of the target component. As a result, the proportion of the amount of the target component to the amount of argon decreases. Thus, the oxidation degree of the target surface corresponds to the amount of the target component present in the plasma. The light transmittance and sheet resistance of the film produced are determined by the thickness of a thin film and the oxidation degree of the metal oxide to be deposited, if the surface condition of the substrate film is constant. Therefore, it is possible to make uniform the light transmittance and sheet resistance of the resultant film, by controlling the rate of oxygen fed to make constant the measurement data of the atomic spectral intensities of the target component and argon or their computation results. It is also possible to form on a substrate film a metal oxide thin film having a constant adhesion to the substrate film, by controlling the anode current so that the atomic spectral intensity of argon is kept in a given range. The use of the above method in a reactive sputtering apparatus for semi-continuous production of a film coated with a metal oxide thin film makes it possible to continuously track the correlation of the atomic spectra of the target component and argon, the light transmittance and sheet resistance of the resulting film and the anode current during the formation of a metal oxide thin film, and thereby to control the light transmittance, sheet resistance and adhesion of the resulting film at higher precisions. As a preferable example of the present process, there can be mentioned the production of a transparent conductive film coated with ITO (indium tin oxide). In the conventional production of such a film, it was necessary to always control the rate of oxygen fed by a skilled labor in order to keep the resistance fluctuation of the resultant film at ±15% in the longitudinal direction and at ±10% in the transverse direction, and the computerized automation using the measurement data of sheet resistance and light transmittance was impossible. The control of adhesion was impossible, either. According to the present invention, by combining a plasma monitor system, a system for measurement of light transmittance and sheet resistance and a feed-back system in the thin film deposition process, it is possible to attain an indium-to-argon ratio giving the lowest sheet resistance and the highest light transmittance in Fig. 2 at a precision of 5% and also to keep the resistance fluctuation of the resulting film at ±5% in the longitudinal direction and at ±5% in the transverse direction. Further, by keeping the fluctuation of atomic spectral intensity (in terms of absolute value) of argon at 5%, it is possible to form a metal oxide thin film having a substantially uniform adhesion to the substrate film. Furthermore, the "in situ" observation of the generated plasma makes it possible to counter even the sudden change of the thin film deposition condition caused by degassing from the film and thereby to prevent the formation of inferior products. Example There is explained a case of producing a transparent conductive film coated with ITO. Fig. 1 shows an apparatus for formation of the film. The vacuum in the closed vessel (1) was controlled at 1.3332 10⁻³ - 1.3332 10⁻⁵ Pa (10⁻⁵ - 10⁻⁷ Torr); the film (2) was run at a constant speed of 0.1 - 3.0 m/min, the film temperature-controlling drum (3) was set at 50 - 200°C; argon was introduced into the closed vessel (1) until the vacuum therein became 1.3332 · 10⁻² - 1.3332 Pa (10⁻⁴ - 10⁻² Torr); a voltage was applied to the target (5) so that the current density to the target area became 20 - 30 A/m²; and oxygen was introduced into the closed vessel (1) from the oxygen tank (7) at a rate of 4/5 to 5/6 of the rate which was believed to be optimum according to experiences. Then, the rate of oxygen fed was changed by the massflow controller (6), and there was obtained the relationship between (a) sheet resistance or light transmittance and (b) ratio of atomic spectral intensity of indium to that of argon, as shown in Fig. 2. By feeding the optimum ratio of atomic spectral intensity of indium to that of argon obtained by the arithmetic unit (8) to the massflow controller (6) for oxygen to make the ratio constant, the fluctuation of the resistance of the resultant film could be reduced to 5% as compared with the fluctuations of ±15% in the longitudinal direction and ±10% in the transverse direction, of the film produced by the conventional process using manual control of oxygen. Further, the control of the anode current based on the relationship between adhesion and atomic spectral intensity of argon could reduce the fluctuation of adhesion to half of that in the conventional process. It is to be noted that the relationship in Fig. 2 may show a minute change with time, and therefore, when a film of strict uniformity is desired, it is necessary to always grasp the exact relationship between (a) sheet resistance or light transmittance and (b) ratio of atomic spectral intensity of indium to that of argon. In this case, it becomes necessary to change the optimum ratio of atomic spectral intensity of indium to that of argon in accordance with the change of the relationship in Fig. 2. The apparatus used in the present invention has made it possible to grasp the minute change of the relationship in Fig. 2 immediately after the start of thin film deposition and to make a tracking correction for the optimum ratio of atomic spectral intensity of indium to that of argon by using a computer.

Claims: A process for semi-continuously producing a transparent conductive film (2) coated with a metal oxide thin film which has a uniform light transmittance, a uniform sheet resistance and a uniform adhesion, which process comprises (a) using a semi-continuous roll (15) to roll (16) sputtering apparatus for a substrate film (2) which comprises a plasma emission spectroanalysis system (13), a system for measuring the light transmittance (12) and sheet resistance (11) of the resulting film and a system for feeding the measurement data of the above two systems to a controller (6) for the rate of oxygen fed or the discharge current or power, (b) measuring the light transmittance and sheet resistance of the film (2) produced as well as the atomic spectral intensities of the target (5) component and argon present in the vicinity of the target (5) surface, and (c) controlling the rate of oxygen fed or the discharge power or current so that the measurement data of the atomic spectral intensities of the target (5) component and argon or their computation results are kept constant and further simultaneously controlling the anode (4) current so that the atomic spectral intensity of argon is kept in a given range, in order to keep the light transmittance and sheet resistance of the resultant film (2) in the respective predetermined ranges and to keep a good adhesion between the substrate film and thin film. A process according to Claim 1, wherein the substrate film (2) is a film of polyether sulfone (PES), polyethylene terephthalate (PET), polyimide (PI), polyether imide (PE), or polycarbonate (PC). A process according to Claim 1, wherein the target (5) component is In, Sn, indium-tin alloy, Si, Ti, Ce or Zn.

Inventors: NAKAMURA, KENJI
Applicants: SUMITOMO BAKELITE COMPANY LIMITED
Application year: 1989
Main classification: C23C14
IPC codes: C23C14, H01L31