JP2002329701A - Semiconductor substrate, display device using the same, method of manufacturing the same, and manufacturing apparatus - Google Patents

Abstract

(57) [Summary] The main part of the above manufacturing process is the display device manufacturing process, the instability of device characteristics due to substrate contamination caused by cross-contamination caused by the environment of a clean room or cross-contamination caused by the regenerating solution of chemicals used, etc. Manage cleaning between processes. SOLUTION: The present invention relates to a silicon film surface which is exposed after an oxide film on a substrate is removed by etching and cleaned,
It is characterized in that the surface of the natural oxide film covering the metal film on the substrate and the surface of the insulating film formed by the film are cleaned, and the film surface is modified by hydrogen treatment. This has the following effect. In other words, the present invention provides a semiconductor substrate having good characteristics by maintaining the cleanliness of the film surface by modifying and stabilizing the film surface on the substrate, thereby maintaining the lamination interface clean. .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate processing method and a manufacturing apparatus for a process of manufacturing an electronic component using a substrate.

[0002]

2. Description of the Related Art A conventional method will be described below by taking a method of manufacturing a liquid crystal display as an example.

[0005] In general, the manufacture of a TFT substrate as a liquid crystal display device is performed between processes such as cleaning before film formation and cleaning before and after pattern processing (FIG. 6). Many of its cleaning purposes are to remove particles and contaminants. TFT
Is composed of a metal film, an insulating film and a semiconductor layer, and the surface of the metal film and the semiconductor layer is covered with a natural oxide film. Generally, a wet cleaning method based on RCA cleaning using a chemical solution based on a hydrogen peroxide solution known in the semiconductor process is used.

H ₂ S used for stripping semiconductor resist
O ₄ / H ₂ O ₂ (SPM) cleaning is a method of oxidizing and removing organic substances. Also, NH ₄ OH / H ₂ O ₂ (APM) cleaning is used for particle removal, and HCl / H ₂ O ₂ (HPM) cleaning is used for removing metal contamination. Since most of these RCA cleanings are performed at a high temperature, the composition of the liquid changes remarkably, and liquid management and cleanness control in a clean room due to evacuation of evaporated components are required.

It is extremely difficult to clean a large substrate such as a liquid crystal substrate with a chemical solution under the above-mentioned high temperature control.
Single-wafer processing using an organic cleaning liquid or a hydrofluoric acid aqueous solution and using pure water as a rinsing liquid is performed. The hydrofluoric acid aqueous solution can remove deposits on the substrate surface by etching the natural oxide film.
Further, the organic matter can be removed by decomposing and vaporizing the substrate by exposing the substrate to ozone gas. Recently, ozone water in which ozone gas is contained in pure water has attracted attention as a functional water instead of the RCA cleaning. Ozone water oxidizes metal and organic deposits on the substrate surface with ozone gas, and cleans the substrate surface by etching the oxide with dilute hydrofluoric acid aqueous solution. However, the liquid crystal display device is composed of a stack of thin films, and performing a cleaning method using a dilute hydrofluoric acid aqueous solution and pure water for all inter-step cleaning in a full TFT process requires the controllability of the film thickness. Unsuitable from. Also, in the step of forming the metal wiring, the oxidizing property of the ozone water was unsuitable depending on the kind of metal.

Further, if the contaminants in the clean room are adsorbed on the substrate surface due to exposure to the environment of the clean room and are confined in the next step and remain at the interface, the device characteristics are degraded.

[0007] Contaminants floating in the clean room are adsorbed and contaminated on the substrate as follows. Contaminants are emitted from the clean room constituent materials, and the clean room air-conditioning filter (HEPA filter) made of glass material also dissolves the filter by circulating the clean room atmosphere in the chemical use process and becomes fine particles and floats in the clean room. I do.

In the configuration of the liquid crystal display device, if the above-mentioned contaminants are adsorbed, they diffuse into the semiconductor layer via plasma processes or thermal processes or remain at the interface, causing poor film characteristics. At the particle size level, the residue between layers causes coverage and pattern defects,
This causes various problems such as insulation failure and breakdown voltage failure. Furthermore, in the completed TFT, there is a problem that a variation occurs due to the application of the driving voltage, which causes a variation in initial characteristics and further a deterioration variation in reliability characteristics.

[0009]

SUMMARY OF THE INVENTION
For the instability of device characteristics due to substrate contamination caused by cross-contamination caused by a clean room environment or a regenerating solution of a used chemical, cleaning between main steps of the manufacturing process is controlled.

[0010]

According to the present invention, there is provided a semiconductor substrate comprising:
A semiconductor substrate having an oxide film, wherein part or all of the oxide film is removed and reformed by hydrogen treatment. Further, the semiconductor substrate is at least made of silicon.

Another semiconductor substrate of the present invention is a semiconductor substrate having a metal film and a natural oxide film surface coated with the metal film, wherein the natural oxide film is cleaned and modified by hydrogen treatment. A semiconductor substrate.

Another semiconductor substrate of the present invention is a semiconductor substrate having an insulating film formed by film formation, wherein the surface of the insulating film is cleaned and modified by hydrogen treatment. It is a substrate.

According to the invention of the semiconductor substrate described above, the film surface on the substrate is modified and stabilized to maintain the cleanliness of the film surface, and furthermore, the semiconductor interface having good characteristics by keeping the lamination interface clean. A substrate can be provided.

Further, the display device of the present invention, a liquid crystal display device,
Alternatively, an organic EL display device uses the semiconductor substrate described in any of the above.

According to the above invention, in addition to the device characteristics, there are effects of good display characteristics, stabilization of reliability characteristics, and improvement of yield. It has the effect of measuring stability.

Further, the method for manufacturing a liquid crystal display device according to the present invention includes a cleaning step of removing a part or all of an oxide film;
A method for manufacturing a liquid crystal display device, comprising at least a step of cleaning a natural oxide film surface coated with a metal film, a step of cleaning an insulating film surface by forming a film, and a hydrogen treatment step for modifying the clean surface.

Further, the method of manufacturing an organic EL display device according to the present invention comprises a cleaning step of removing a part or all of an oxide film, a cleaning step of a natural oxide film surface coated with a metal film, and a film formation. Organic EL having at least a step of cleaning the surface of an insulating film by hydrogenation and a step of hydrogen treatment for reforming the clean surface
A method for manufacturing a display device.

Further, the magnetic head of the present invention is a magnetic head comprising a substrate having a natural oxide film surface coated with a metal film cleaned and the film surface modified by hydrogen treatment.

Further, the method of manufacturing a magnetic head of the present invention
A method for manufacturing a magnetic head, comprising: a step of cleaning the surface of a natural oxide film at each interface of a multilayer film constituting the electrodes and elements and performing a hydrogen treatment on the film surface when forming electrodes and elements on an MgO substrate. . Further, the hydrogen treatment is a method of manufacturing a magnetic head, wherein hydrogen treatment is performed by hydrogen gas dissolving method or pure water electrolysis method.

According to the invention relating to the magnetic head, the cleanliness is maintained by performing hydrogen treatment after cleaning the electrode interface and the underlayer interface of the laminated film, and the short-circuit between the electrodes is prevented without forming the depletion layer. It has the effect of doing.

In the hydrogen treatment of the present invention, the substrate is exposed to hydrogen gas, or the substrate is treated using water hydrated by a hydrogen gas dissolving method or a pure water electrolysis method.

The manufacturing apparatus of the present invention includes at least a cleaning unit for removing organic substances, oxidized substances, inorganic substances, ionic substances, and the like during substrate cleaning, and a unit for modifying the substrate surface. Become. In the cleaning unit, for example, the substrate surface is oxidized by ozone water or etched by dilute hydrofluoric acid, the substrate surface residual solvent is replaced by pure water, and the substrate surface is cleaned, and in other units, the substrate surface is cleaned. The substrate is held, and the surface of the substrate is subjected to a reforming process.

[0023]

Embodiments of the present invention will be described below with reference to the drawings.

(First Embodiment) An embodiment of the present invention will be described with reference to a schematic manufacturing flow of a liquid crystal display device (see FIG. 1) as an example. Hydrogen treatment for cleaning using hydrogen-containing water (hydrogen water) is performed after various conventional cleaning steps.

FIGS. 7 and 8 show the results of experiments using, for example, a silicon substrate as the substrate. "Wash-A" on the left side of FIG.
Is the residual amount of fine particles after washing using conventional pure water. On the other hand, “cleaning-B” on the right side of FIG. 7 shows the residual amount of fine particles after cleaning using hydrogen-containing cleaning water instead of pure water. This is a known result that hydrogen-containing water has excellent particle removal performance in substrate cleaning. Note that although a silicon substrate is used in this embodiment mode, another material or form (substrate, electrode, or film) such as aluminum, titanium, tungsten, copper, silver, molybdenum, palladium, or an alloy thereof, or ITO (Ind
ium Tin Oxide), SiOx, SiNx,
Similar effects can be obtained with oxides such as AlOx and TiOx.

FIG. 8 shows the result of examining the process of contamination on the substrate surface by repeating washing and particle contamination on the substrate.
Shown in In the conventional pure water cleaning, the effect of removing fine particles by cleaning is dilute, and the amount of fine particles remaining on the substrate surface tends to increase due to repeated contamination. In addition, when a repeated experiment of cleaning and particulate contamination was performed on the SiOx film surface including the natural oxide film covering the metal film and the like in the same manner as above, the result was similar to the Si surface (see FIG. 9).

Next, the surface of the SiOx film was exposed to organic matter for contamination, and the change in the contact angle was examined as the number of exposure days and the state of the surface of the SiOx film. Was confirmed (see FIG. 10).

On the other hand, it has been proved that it is effective to prevent the re-contamination of the clean substrate surface and to subject the contaminants to hydrogen termination by subjecting the substrate surface to hydrogen treatment after the main cleaning process. Was. Therefore, an object of the present invention is to provide a manufacturing method and a manufacturing apparatus in which the hydrogen treatment of the present invention is added after a cleaning step in a TFT manufacturing process, and a semiconductor substrate obtained thereby.

The experimental results that led to the above proof will be described below with reference to FIGS.

FIG. 2 shows a case where the particulate contamination substrate is again subjected to particulate contamination after the cleaning process. With respect to Washing-B, the amount of re-contamination was slightly small, and the effect of preventing re-adhesion of fine particles was confirmed.

Next, FIG. 3 shows the amount of residual fine particles on the substrate surface by repeating fine particle contamination and cleaning on the Si surface. As compared with the washing-A (pure water), the washing-B (hydrogen-containing water) showed an increase in the residual amount due to repetition, but the removal effect was confirmed every washing.

Next, FIG. 4 shows the amount of residual fine particles on the substrate surface by repeating fine particle contamination and cleaning on the SiOx film surface in the same manner as described above. Compared with Cleaning-A (pure water), Cleaning-B (hydrogen-containing water) showed a slight increasing tendency by repetition, but an extremely good cleaning and removing effect up to the initial value level could be confirmed. Although hydrogen-containing water was used as an example for "Washing-B", its production method is not limited. Further, other solvents or gases may be used as long as the H (hydrogen) terminating effect can be obtained. Also, the manufacturing flow used in the present invention is an example, and it goes without saying that the effect of hydrogen treatment after the cleaning step remains unchanged although the steps may differ depending on the device configuration. In the embodiment of the present invention, it is needless to say that the effect is enhanced by the combined use of a chemical solution and functional water as long as the removal promotion and the reattachment of the detached particles can be controlled.

Next, the surface of the SiOx film was subjected to exposure to organic matter, and the change in the contact angle was examined as the number of exposure days and the state of the surface of the SiOx film. The conventional cleaning-A was contaminated in about 3 days. In contrast, in the case of cleaning-B, it was confirmed that the substrate surface was stable up to 10 days (see FIG. 5).

These hydrogen treatments are performed by using Si or Si--O on the substrate surface.
On the other hand, it is an effect that the substrate surface can be stably modified by H (hydrogen) bond.

As described above, it was confirmed that by performing the rinsing treatment after the cleaning as the cleaning-B, the margin of the manufacturing process, that is, the stability of the cleaned substrate is expected to improve the performance and productivity.

(Second Embodiment) A second embodiment is a display device using the cleaned substrate described in the first embodiment. It is characterized in that it has the substrate state described in the first embodiment in the process of manufacturing while repeating processes such as film formation and pattern processing, and modifies and stabilizes the film surface on the substrate. Display devices using substrates that maintain the cleanliness of the film surface by this, and thus keep the lamination interface clean,
It has good display characteristics in addition to device characteristics.

(Third Embodiment) A third embodiment is an organic EL display device using the cleaned substrate described in the first embodiment. In the process of manufacturing while repeating processes such as film formation and pattern processing, the first
Characterized in that it has the substrate state described in the embodiment, and the film surface on the substrate is modified and stabilized to maintain the cleanliness of the film surface, and thus keep the lamination interface clean. A display device using a substrate has good display characteristics in addition to device characteristics.

(Fourth Embodiment) A conventional electrode for an ink jet head which has been washed with a surfactant or pure water is a laminated film composed of layers of Pt, PLT, PZT and the like.
In the process of manufacturing this laminated film, a depletion layer due to particles was generated between the layers, and when the depletion layer was formed, ink entered the depletion layer, causing a short-circuit between electrodes. The present invention has an effect of maintaining cleanliness by performing a hydrogen treatment after cleaning the electrode interface and the underlying interface formed of the laminated film according to the present invention, and preventing a short-circuit between electrodes without forming the depletion layer. is there.

(Fifth Embodiment) In a fifth embodiment, a cleaning unit for removing organic substances, oxidized substances, inorganic substances, ionic substances, etc. in cleaning a substrate, and a modification of the substrate surface are provided. This is a manufacturing apparatus comprising at least a unit for quality control. And it keeps the film surface clean during the process of manufacturing the substrate for the display device,
In addition, it is characterized by the substrate surface treatment of a substrate whose lamination interface is kept clean, and by modifying and stabilizing the film surface on the substrate,
To obtain the substrate state described in the fourth to fourth embodiments.

[0040]

According to the present invention, the hydrogen treatment is performed on the surface of the substrate.
The substrate surface can be stably reformed by H (hydrogen) bond to i or Si-O, preventing the re-adhesion of contaminants and improving the adhering substance removal property, thereby stabilizing the manufacturing environment and improving productivity. Can be done.

[Brief description of the drawings]

FIG. 1 is a schematic manufacturing flowchart of the present invention.

FIG. 2 is a diagram for confirming the hydrogen treatment effect of the present invention.

FIG. 3 is a diagram for confirming the hydrogen treatment effect of the present invention.

FIG. 4 is a diagram for confirming the hydrogen treatment effect of the present invention.

FIG. 5 is a diagram for confirming the hydrogen treatment effect of the present invention.

FIG. 6 is a block diagram of a cleaning / surface reforming apparatus according to the present invention.

FIG. 7 is a flowchart of a conventional schematic manufacturing process.

FIG. 8 is a diagram showing a conventional hydrogen treatment effect

FIG. 9 is a diagram showing a conventional hydrogen treatment effect

FIG. 10 is a diagram showing a conventional hydrogen treatment effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G11B 5/31 G11B 5/31 A 5F110 G 5G435 H01L 21/336 H05B 33/02 29/786 33/14 A H05B 33/02 H01L 29/78 612Z 33/14 627Z (72) Inventor: Mutsumi Yamamoto 1006, Ojidoma, Kadoma, Osaka Prefecture F-term in Matsushita Electric Industrial Co., Ltd. BB96 CC01 3K007 AB11 AB18 BA06 BB07 DA01 DB03 EB00 FA01 5C094 AA42 AA43 BA29 EB05 GB10 5D033 BA51 DA31 5F110 AA14 AA26 EE47 FF35 GG02 GG13 GG51 GG57 HJ21 HL26 NN39 NN40 5G435 AE33

Claims (17)

[Claims] 1. A semiconductor substrate having an oxide film, wherein part or all of the oxide film is removed and cleaned, and the substrate surface is modified by hydrogen treatment. 2. The semiconductor substrate according to claim 1, wherein said semiconductor substrate contains at least silicon. 3. A semiconductor substrate having a metal film and an oxide film surface coated with the metal film, wherein the oxide film is cleaned and modified by a hydrogen treatment. 4. A semiconductor substrate having an insulating film formed by film formation, wherein the surface of the insulating film is cleaned and modified by a hydrogen treatment. 5. A display device using the semiconductor substrate according to claim 1. Description: 6. A cleaning step for removing a part or all of an oxide film, a cleaning step for a natural oxide film surface coated with a metal film, a cleaning step for an insulating film surface by forming a film, and the cleaning step. A method for manufacturing a display device comprising at least a hydrogen treatment step for modifying a surface. 7. A liquid crystal display device using the semiconductor substrate according to claim 1. Description: 8. A cleaning step for removing a part or all of an oxide film, a cleaning step for a natural oxide film surface coated with a metal film, a cleaning step for an insulating film surface by forming a film, and the cleaning step. A method for manufacturing a liquid crystal display device having at least a hydrogen treatment step for modifying a surface. 9. An organic EL display device comprising a semiconductor substrate according to claim 1, comprising an organic light emitting material and a current driver. 10. A cleaning step for removing part or all of an oxide film, a cleaning step for a natural oxide film surface coated with a metal film, a cleaning step for an insulating film surface by forming a film, and the cleaning step. A method for manufacturing an organic EL display device having at least a hydrogen treatment step for modifying a surface. 11. A magnetic head comprising a substrate in which a surface of a natural oxide film coated with a metal film is cleaned and the film surface is modified by hydrogen treatment. 12. A magnetic head comprising the steps of: when forming an electrode or an element on an MgO substrate, cleaning the surface of the natural oxide film at each interface of a multilayer film constituting the electrode or the element, and subjecting the film surface to a hydrogen treatment. Manufacturing method. 13. The hydrogen treatment is performed by using water which has been hydrogenated by a hydrogen gas dissolution method or a pure water electrolysis hydrogen dissolution method, or by exposing to a hydrogen gas atmosphere. A method for manufacturing a magnetic head according to claim 12. 14. The hydrogen treatment is characterized in that the treatment is carried out using water hydrogenated by a hydrogen gas dissolving method or a pure water electrolytic hydrogen dissolving method, or by exposing to a hydrogen gas atmosphere. A method for manufacturing a display device according to claim 6. 15. The hydrogen treatment is characterized in that the hydrogen treatment is carried out using water which has been hydrogenated by a hydrogen gas dissolving method or a pure water electrolysis hydrogen dissolving method, or is exposed to a hydrogen gas atmosphere. A method for manufacturing a liquid crystal display device according to claim 8. 16. The hydrogen treatment is characterized in that the hydrogen treatment is carried out using water hydrogenated by a hydrogen gas dissolving method or a pure water electrolysis hydrogen dissolving method, or by exposing to a hydrogen gas atmosphere. A method for manufacturing an organic EL display device according to claim 10. 17. A manufacturing apparatus comprising at least a cleaning section for removing an organic substance, an oxidized substance, an inorganic substance, an ionic substance and the like in cleaning a substrate, and a section for modifying the surface of the substrate.