CN1544688A

CN1544688A - Plasma reinforced chemical vapor deposition apparatus for transparent conductive film

Info

Publication number: CN1544688A
Application number: CNA2003101109126A
Authority: CN
Inventors: 冯良桓; 奚建平; 雷智; 蔡伟; 郑家贵; 王钒
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2003-11-12
Filing date: 2003-11-12
Publication date: 2004-11-10
Anticipated expiration: 2023-11-12
Also published as: CN1317422C

Abstract

The invention is a 'transparent conductive film's plasma enhanced chemical gas-phase deposition device'. It is a technique of implementing special metal-oxide film fabrication, makes a special effort to solve the problems of good performance of large-area film, uniform thickness, waste gas discharge, etc. Its character: it sets special uniform pressure spout, uses grounding electrode to fully screen radio frequency electrode and installs cold trap to collect reacting waste gas. It is applied to large-area fabrication of multiple oxide films.

Description

Plasma enhanced chemical vapor deposition equipment for transparent conductive film

One, the technical field

The invention belongs to large-scale production equipment for photoelectric functional materials

Second, background Art

The transparent conductive film is a photoelectric functional material with an increasingly wide application range, and is particularly important in application to solar cells and displays. At present, ITO and SnO are transparent conductive films commonly used₂、ZnO、 CdSnO₄The preparation method comprises magnetron sputtering, low-pressure chemical vapor deposition and normal-pressure chemistryVapor deposition, spray pyrolysis, and the like. These methods are already available for large scale production and therefore large scale plants have been used to carry out these methods.

The transparent conductive film prepared by the magnetron sputtering method is best in transmittance, conductivity and uniformity. However, this method has a low deposition rate and high manufacturing cost, and it is difficult to manufacture a target having a large area. The transparent conductive film prepared by low-pressure chemical vapor deposition and normal-pressure chemical vapor deposition has good quality, but the deposition temperature is higher, and the uniformity on a large area is not easy to solve. Spray pyrolysis (including ultrasonic spray pyrolysis) is a developing technology, and the quality of the film is not stable enough, the thickness is not uniform enough, and the surface of the film is not flat enough at present.

On the other hand, plasma enhanced chemical vapor deposition techniques have been used to deposit amorphous silicon, polysilicon, silicon carbide films. But is also a new technique for depositing transparent conductive films. The basis of this technique is the following reaction

Some of the above reactions can be carried out at room temperature, but to form good quality oxide films, the reaction temperature and deposition temperature are generally above 500 ℃. The plasma promotes the reaction, so that a transparent conductive film with excellent quality can be deposited even when the substrate temperature is low. The polycrystalline film, the nanocrystalline film and the amorphous film can be respectively deposited by matching with the change of the temperature of the substrate. Their properties, in particular electrical and optical properties, vary greatly.

In the existing plasma enhanced chemical vapor deposition equipment, the technology of depositing a large-area film is solved, and in large-scale production, two methods are adopted, namely a multi-chamber system for depositing a sample at a time, wherein each chamber has different functions such as pre-vacuum, preheating, deposition, cooling and the like. The complex coefficient of the equipment is higher, and the manufacturing cost is high. Another method is a one-chamber multi-chip system, and now each pair of electrodes has a radio frequency power supply and a matcher, and the equipment is expensive.

Third, the invention

The invention aims to design a device which can deposit a large-area transparent conductive film by using a plasma enhanced chemical vapor deposition method and is suitable for large-scale production.

The structure of the transparent conductive film plasma enhanced chemical vapor deposition device is shown in figure 1. A1 is a vacuum chamber, B1, B2 and B3 are plate heaters. C1 and C2 are electrodes, grounded. D1 and D2 are insulating plates. E1 and E2 are electrodes, which are connected to a radio frequency high voltage. Heating plate B3 was equal to or less than heating plates B1 and B2 in both length and width; the electrodes E1 and E2 were smaller in both length and width than the insulating plates D1 and D2, and D1 and D2 should wrap the edges of the high-frequency electrodes E1 and E2. S is the sample. The positions of the plate-shaped heaters B1 and B2 or the electrodes C1 and C2 may be adjusted in the horizontal direction to change the distances from the high voltage rf electrodes E1 and E2, respectively. F1 and F2 are pressure equalizing chambers having gas inlets G1 and G2, respectively, and for typical chemical vapor deposition, the same gas is introduced into both chambers through G1 and G2. As shown in fig. 2, the upper half of the inner wall of the two chambers has a row of small holes through which the reaction gas enters the space K above the electrodes. A pressure equalizing cavity F3 is arranged between F2 of F1, and an air inlet H is arranged at the upper part of the F3; the other reactant gas enters the space K via F3. Thus, in effect, K is an open gas mixing chamber. M1, M2 and M3 are thermocouples respectively.

I1 is the pumping hole of the vacuum chamber, L1 is the stop valve, J is the cold trap. And the waste gas after reaction passes through a cold trap J and then enters a vacuum pump. The role of the cold trap is important. The above equation shows that for some reactions, HCl is formed. The gas is an active gas and has strong corrosivity at high temperature, so that the temperature of the gas is firstly reduced as much as possible and then the gas is discharged or treated; even solidified in a cold trap and then processed. JQ is the collector.

The system described herein is characterized by depositing 4 samples at a time using a single chamber configuration. However, the auxiliary processes of breaking the vacuum, loading the sample, obtaining the vacuum, heating the sample, etc. take a considerable time, and the manufacturing efficiency is lowered. To this end, the present invention further proposes a two-chamber structure, as shown in fig. 3. The vacuum chamber A2 and its internal configuration are identical to those of the vacuum chamber A1 and its internal configuration. For A2, the pumping port is I2, and the cold trap J is accessed through a stop valve L2. Thus, the two-chamber structure of the present invention has no mechanism for driving the sample, but shares a radio frequency power supply, a cold trap and a mechanical pump. In use, when the A1 works, the A2 is in a state of taking, loading a sample and waiting; next, a2 was in operation, a1 was in a sample, and wait state. Thus, only one identical reaction chamber is added, doubling the production efficiency.

The invention has the following advantages:

1. an apparatus for manufacturing a transparent conductive film is developed. The technique used by such an apparatus is plasma enhanced chemical vapor deposition. Compared with the prior art such as sputtering, low-pressure chemical vapor deposition and atmospheric pressure chemical vapor deposition, the technology has the advantages of low deposition temperature, higher resistivity (because the film is in an amorphous structure), more uniform thickness and the like.

2. The special air inlet nozzle is provided, and the uniformity of the prepared film is ensured by adding the uniform glow discharge effect.

3. And the low-temperature cold trap is adopted to collect waste gas,so that subsequent equipment and environment are protected.

4. The device has a relatively simple structure and high production efficiency of samples. Especially, the double reaction chamber system does not need a complex transmission mechanism, and the radio frequency power supply and the vacuum system are utilized most effectively, so that the production efficiency is doubled.

Description of the drawings

FIG. 1 shows the basic structure of the present invention

FIG. 2 is an air inlet nozzle structure of the present invention

FIG. 3 shows the basic structure of a two-chamber system according to the present invention

FIG. 4 is another configuration of the air intake nozzle of the present invention

Fifth, detailed description of the invention

Example 1: as shown in FIG. 1, vacuum chamber A1 is made of carbon steel and is formed in a conventional box coater configuration with a front door. The plate heaters B1, B2 and B3 are vacuum insulated heating devices, i.e. all electrical connections are not exposed to the vacuum chamber to avoid creating a low pressure discharge. The electrodes C1, C2, E1 and E2 are stainless steel plates 2-4 mm thick. The electrodes E1 and E2 should have the same shape as the substrate of the sample, with dimensions slightly larger than the latter. The insulating plates D1 and D2 are made of corundum porcelain, the thickness is 2-3 mm, the surfaces are smooth, and a mirror surface is not needed. Examples of dimensions of the entire electrode system are as follows: sample size 300X 400X 3mm³And the dimensions of the electrodes E1 and E2 were 300(height). times.400 (length). times.3 mm³And the dimensions D1 and D2 are 346 (height) x 446 (length) x 3mm³The area of the plate-shaped heater is 346 (height) x 446 (length) mm²After the sample is arranged, the surface space S of the sample is adjustable between 8mm and 100mm, and the sizes of the grounding electrodes C1 and C2 are 350 (height) multiplied by 450 (length) multiplied by 3mm³。

The power of the plate heater is set according to the following temperature requirements: the electrode temperature was 350 ℃ and the sample surface temperature was 250 ℃.

As shown in fig. 2, the reaction gas inlet nozzle is made of stainless steel. In fact, the compound pressure equalizing spray head is formed by three cavities which are parallel to each other. The sides are substantially an isosceles right triangle plus a rectangle. The specific dimensions are as shown in the figure: d is 440mm, h is 60mm, l is 220 mm. The cross-section can be seen to consist of three cavities, the total width of which corresponds to the spacing between electrodes C1 and C2 in fig. 1, i.e. k is around 100 mm. The lower bottom surfaces of the three cavities are provided with nozzles, the distribution of the nozzles is shown by a bottom view, and the nozzles of the middle cavity are positioned in the centers of squares formed by the nozzles of the two side cavities. To increase the area of contact between the two reactant gases. The hole diameter is 4mm, and the hole pitch a is 8 mm.

The cold trap J uses liquid nitrogen as the working substance. One of the gases from the reaction chamber, HCl, had a freezing point of-114.8 c and could solidify in the cold trap without entering the vacuum pump and atmosphere. After the reaction was complete, HCl was in a liquid state between-114.8 ℃ and-84.9 ℃ and flowed into accumulator JQ. The JQ is connected with the J by a quick sealing joint, and the JQ can be taken down and cleaned by water and then installed and restored.

Example 2: in example 1, the vacuum chamber was composed of a vacuum hood and a bottom plate. After the vacuum is broken, the vacuum hood is lifted by a lifting device.

The area of electrodes E1 and E2 is 2, 3, 4 or more times greater than the area of the sample. At a sample area of 300X 400mm²In the case of (2), the areas of the electrodes E1 and E2 were 440X 640mm². The area of the electrodes C1 and C2 was 480X 680mm². When the samples are placed, the two samples are close together without leaving a gap. The pressure equalizing head has the same structural shape as in example 1. d should be slightly longer than 600mm and should remain l-d/2. The diameter and the interval of the circular jet holes can be kept constant, and the number of the circular jet holes needs to be increased correspondingly. In order to improve uniformity, the pressure equalizing showerhead can be formed by stacking 5 chambers instead of three chambers, and the structures of the pressure equalizing showerhead are H, G3, G4, G5 and G6 which are all reaction gas inlets as shown in FIG. 4, and G5 and G6 can also introduce protective gas which does not participate in reaction. With this configuration, 8 samples can be deposited at a time, or more samples can be deposited.

Example 3: in embodiment 1, the heaters B1, B2, and B3 may be omitted. Accordingly, the insulating plates D1 and D2 may be eliminated and the electrodes E1 and E2 combined into one electrode plate. Such an apparatus is suitable for deposition processes that do not require heating of the substrate. The cold trap J is refrigerated by Freon or magnetic refrigeration.

Example 4: in example 2, the electrode panel was enlarged to improve the production efficiency. However, this can cause problems with the uniformity of the sample. Therefore, another method can be adopted, namely according to embodiment 1, make a reaction chamber more, two reaction chambers structure and size and in embodiment 1A 1 exactly the same, as shown in figure 3. The reaction gas paths are independent. The waste gas outlets I1 and I2 respectively pass through valves L1 and L2 and then are collected in a gas path to enter the cold trap J. The RF power source is also only one set, and can be switched to the reaction chambers A1 and A2 respectively. If the geometrical configuration of the two reaction chambers is identical, the adapter for the radio frequency power supply can also be one. When the reaction chamber on the left is in operation, the radio frequency power supply is switched to A1, the I1 and L1 are switched on, and the I2 and L2 are switched off; the reaction chamber on the right carries out the operation of taking and placing the sample. When the reaction chamber on the right side works, the radio frequency power supply is switched to A2, the I2 and L2 are switched on, and the I1 and L1 are switched off; the reaction chamber on the left is used for taking and putting samples.

Claims

1. The equipment for preparing transparent conducting film is characterized by that it has a set of vacuum system with high-voltage radio-frequency power supply to implement plasma-enhanced chemical vapour deposition technology, and can prepare several large-area samples at one time.

2. The apparatus for producing a transparent conductive film according to claim 1, wherein a cold trap is provided between the vacuum system and the vacuum pump to cool an exhaust gas discharged from the processing chamber.

3. The apparatus for preparing a transparent conductive film according to claim 1, wherein a composite voltage-sharing nozzle slightly longer than the electrode is provided above the electrode, and the front surface of the composite voltage-sharing nozzle is shaped like a right isosceles triangle. The specific structure is that three pressure equalizing cavities with the same shape are superposed, one reaction gas is introduced into the middle cavity, and the other reaction gas is introduced into the two outer cavities. The bottom of each cavity is provided with a string of uniformly distributed spray holes.

4. A composite pressure equalizing sprinkler as defined in claim 3, which is formed by stacking five pressure equalizing chambers having the same shape. Three reaction gases can be symmetrically introduced into each pressure equalizing cavity, and protective gases which do not participate in the reaction can also be introduced into the outermost two cavities.

5. The apparatus for manufacturing a transparent conductive film according to claim 1, wherein the back surface of the ground electrode has a plate-like heater having the same shape and size as the ground electrode. Between two radio frequency power supplies, two side faces of the plate-shaped heater are provided with high-performance insulating plates.

6. The electrode of claim 5, wherein a plate heater is not required. All three electrodes are simplified to metal plates.