JP2006261633A - Substrate processing method, solid-state imaging device manufacturing method, thin-film device manufacturing method, and program - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate processing method capable of accurately controlling the removal amount of an insulating film without damaging an electronic device.
In order to manufacture a CCD sensor, an insulating film 251 is formed on a wafer W on which photoelectric conversion elements 210 are formed in a matrix, a conductive film is formed, and etching is performed using a photoresist layer. A transfer electrode 221 is formed. An insulating film and a conductive metal film are formed, and an interlayer insulating film 222 and a light shielding film 223 are formed by etching using a photoresist layer. Next, a silicon nitride film 252 is formed, and an insulating film 261 having a predetermined thickness made of SiO ₂ is formed in order to form a planarizing film 253 having a desired thickness. Then, the wafer W on which the insulating film 261 is formed is exposed to a mixed gas of ammonia gas and hydrogen fluoride gas under a predetermined pressure, and the product denatured from SiO ₂ forming the insulating film 261 is heated to a predetermined temperature. To do.
[Selection] Figure 7

Description

  The present invention relates to a substrate processing method, a solid-state imaging device manufacturing method, a thin film device manufacturing method, and a program, and more particularly to a substrate processing method for polishing an insulating film by a chemical mechanical polishing method.

  As a manufacturing method of a color filter in a solid-state imaging device such as an electronic device, for example, a CCD sensor, a color resist method has been widely put into practical use.

  For example, when forming color filters in the order of green, red, and blue in the formation of color filters, the red or blue color filters that are formed later are inclined to the film thickness due to the influence of the color filters that are formed earlier. Be angry. For this reason, it is difficult to form a color filter with a desired film thickness, and film thickness controllability is lacking. In addition, the thickness of the color filter may vary within a single linear sensor or between multiple linear sensors, and the uniformity of the thickness of the color filter deteriorates macroscopically in a solid-state imaging device. As a result, noise and sensitivity unevenness occur, which causes the characteristics of the line sensor to deteriorate significantly.

  In order to solve the above-described problem, the thickness of the second and third color filters formed in the second color and the third color is conventionally set to 1.3 times the thickness of the first color filter formed in the first color. By making it more than double, even if it overlaps with the first color filter at the peripheral edge of each pixel without causing a gradient in the film thickness of the second and third color filters in the effective pixel, the overlapped portion and the center portion of the pixel A method for manufacturing a color filter that can suppress the occurrence of a difference in film thickness is disclosed (for example, see Patent Document 1).

  However, in recent years, in the solid-state imaging device, the pixel size has been reduced with the increase in the number of pixels, and the miniaturization technique of the color filter array is indispensable. In addition, it is indispensable to reduce the thickness of the color filter in response to the reduction in the pixel size in order to improve the light collecting property of the solid-state imaging device.

  Since the above-described conventional color filter manufacturing method partitions the color filter array assuming a line width of 10 μm, for example, it is structurally difficult to partition the color filter array to a line width of 1 μm or less. Therefore, it has been difficult to further miniaturize the solid-state imaging device.

  In the color resist method, in order to reduce the thickness of the color filter, it is effective to increase the content ratio of the dye to the photosensitive resin composition as much as possible in the dye-containing photosensitive resin composition to be applied. Conventionally known.

  However, when the content ratio of the dye as the pigment is close to 50%, a desired pattern shape can be obtained by exposure and development, but it is difficult to thermally cure the resin composition. The color filter is required to have solvent resistance to the solvent contained in the resin composition. In the conventional manufacturing method, the resin composition is thermally cured to impart solvent resistance to the color filter. If the resin composition is not heat-cured, the solvent resistance of the color filter is deteriorated, and the resin composition for forming a color filter of another color cannot be applied in the next step. Moreover, in order to give sufficient solvent resistance, when the thermosetting is carried out at a higher temperature (for example, 200 ° C. or more), the color filter reflows or the dye is chemically changed by heat, so that the color filter becomes original. In some cases, spectral characteristics were not exhibited.

In order to solve this problem, there is a color filter manufacturing method in which a color filter is formed by applying a resin composition, and a protective film that is an insulating film such as a silicon oxide film (SiO ₂ ) is formed on each color filter. It is disclosed (for example, see Patent Document 2). As a result, the solvent resistance of the color filter can be increased due to the presence of the protective film without the need to thermally cure the coating film of the resin composition by a high-temperature heat treatment. Since the content ratio of the pigment in the filter can be increased, the color filter can be thinned.

However, in the above-described color filter manufacturing method, the color filter can be thinned, but a low temperature plasma CVD process is required to form a SiO ₂ layer having a thickness of about 50 nm as a protective film on the color filter. There is a problem that the manufacturing time (TAT) becomes long.

  In addition, in the conventional method for producing a color filter, the applied resin composition is irradiated with ultraviolet rays to perform photodecomposition (bleaching) of unnecessary photosensitizers, and further heat cure the resin composition by heat treatment. However, since it is difficult to control the shrinkage rate of the resin composition due to thermosetting, an error occurs in the film thickness of the color filter for each heat treatment. An error in the film thickness of the color filter causes unevenness of the optical axis in the solid-state imaging device, and thus causes color unevenness and image unevenness.

  Some conventional solid-state imaging devices include a microlens on a color filter formed on a planarizing film that is an insulating film via a protective film. When the distance from the light receiving part (photoelectric conversion element) to the microlens is long, that is, when the thickness between the photoelectric conversion element and the microlens is thick, obliquely incident light is shielded by a convex part made of an electrode or the like. As a result, the light condensing property of the solid-state imaging device is lowered. Therefore, it is required to reduce the space between the photoelectric conversion element and the microlens. On the other hand, there is a demand for higher image quality in the color tone of the screen, and accordingly, it is necessary to further improve the quality of the transmitted color spectral characteristics of the color filter. For this purpose, it is necessary to improve the quality of the hue, and the quality of the hue can be improved by increasing the thickness of the color filter. However, increasing the thickness of the color filter is contrary to the above-described demand for thickness reduction.

  Further, due to the miniaturization of the solid-state imaging device, when forming the solid-state imaging device, there is a strong demand for alignment accuracy with respect to the base element in the process of forming an upper layer element such as a color filter or a microlens. This alignment of the upper layer element with respect to the underlying element is performed by detecting the reflected / diffracted light of the laser beam from the alignment mark formed on the underlying element through the planarizing film, thereby aligning the underlying device with the upper layer element. Is going. However, optically misalignment is likely to occur in the detection of the imaging position of the alignment mark through the thick planarizing film or protective film. Therefore, in order to improve the alignment accuracy between the underlying device and the upper layer element, it is required to reduce the thickness of the planarizing film and the protective film.

On the other hand, it is conceivable to reduce the thickness between the photoelectric conversion element and the microlens by thinning the flattening film and the protective film. As a method for thinning the flattening film and the protective film, a method of forming the flattening film and the protective film by an etch back process is conceivable.
JP 2004-31557 A JP 2003-75625 A

  However, when performing an etch-back process, the etching method using plasma damages the etched surface and the electronic device, causing a charge difference between the photosensitive part and the transfer part of the solid-state image sensor, and dark current. This will cause an increase in output. Further, when wet etching is used, there is a problem that it is difficult to control the removal amount of the planarizing film and the protective film, so that the desired film thickness cannot be obtained. As described above, in the conventional substrate processing method, it is difficult to form a planarizing film or a protective film having a desired film thickness without damaging the electronic device.

  An object of the present invention is to provide a substrate processing method, a solid-state imaging device manufacturing method, a thin-film device manufacturing method, and a program capable of accurately controlling the removal amount of an insulating film without damaging an electronic device. There is to do.

  In order to achieve the above object, according to the method for manufacturing a solid-state imaging device according to claim 1, the solid-state imaging device manufacturing method includes: And an insulating film exposure step for exposing to an atmosphere of a mixed gas containing hydrogen fluoride, and an insulating film heating step for heating the insulating film exposed to the mixed gas atmosphere to a predetermined temperature.

  According to a second aspect of the present invention, there is provided a method of manufacturing a solid-state imaging device according to the first aspect, wherein the insulating film exposing step performs a plasmaless etching process on the substrate.

  According to a third aspect of the present invention, there is provided the method of manufacturing a solid-state image pickup device according to the first or second aspect, wherein the insulating film exposure step performs a dry cleaning process on the substrate.

  The method for manufacturing a solid-state imaging device according to claim 4 is the method for manufacturing a solid-state imaging device according to any one of claims 1 to 3, wherein the shape of the insulating film is measured, and the measurement is performed according to the measured shape. And a product generation condition determining step for determining at least one of a volume flow rate ratio of the hydrogen fluoride to the ammonia in the mixed gas and the predetermined pressure.

The solid-state imaging device manufacturing method according to claim 5 is the solid-state imaging device manufacturing method according to any one of claims 1 to 4, wherein the volume flow ratio of the hydrogen fluoride to the ammonia in the mixed gas is: 1 to 1/2, and the predetermined pressure is 6.7 × 10 ^{−2 to} 4.0 Pa.

  The solid-state imaging device manufacturing method according to claim 6 is the solid-state imaging device manufacturing method according to any one of claims 1 to 5, wherein the predetermined temperature is 80 to 200 ° C. .

  The method for manufacturing a solid-state imaging device according to claim 7 is a method for manufacturing a solid-state imaging device, the film thickness determining step for determining a desired film thickness of an insulating film provided on a substrate of the solid-state imaging device, and the insulation A pre-processing shape measurement step for measuring the shape of the film; a processing condition determination step for determining the first processing condition and the second processing condition by comparing the measured shape with the determined film thickness; An insulating film exposure step of exposing the insulating film to an atmosphere of a mixed gas containing ammonia and hydrogen fluoride under a predetermined pressure based on a first processing condition; and the mixed gas based on the second processing condition. And an insulating film heating step for heating the insulating film exposed to the atmosphere to a predetermined temperature.

  The solid-state imaging device manufacturing method according to claim 8 is the solid-state imaging device manufacturing method according to claim 7, wherein a post-processing shape measurement step of measuring a shape of the insulating film after the insulating film heating step; A processing condition changing step of changing the first processing condition and the second processing condition by comparing the shape measured in the post-shape measurement step with the determined film thickness; To do.

  The solid-state imaging device manufacturing method according to claim 9 is the solid-state imaging device manufacturing method according to claim 7 or 8, wherein the first processing condition is a volume flow rate of the hydrogen fluoride with respect to the ammonia in the mixed gas. It is at least one of the ratio and the predetermined pressure, and the second processing condition is the predetermined temperature.

  The method for manufacturing a solid-state imaging device according to claim 10, wherein a plurality of photoelectric conversion elements provided in a matrix on a substrate, an insulating film formed on the substrate provided with the plurality of photoelectric conversion elements, A signal charge transfer electrode composed of a switching element and a wiring, formed adjacent to the photoelectric conversion element, an interlayer insulating film formed on the signal charge transfer electrode, and the interlayer insulation on the signal charge transfer electrode A solid-state imaging device manufacturing method comprising a light shielding film made of a metal film formed through a film, the metal film forming step for forming the metal film to form the light shielding film, and the film formation A resist patterning step for forming a resist having a predetermined pattern for forming the light-shielding film on the metal film, and the interlayer using the resist to the vicinity immediately above the metal film and the photoelectric conversion element. A patterning step for patterning the edge film by dry etching to form the light shielding film and the hole, a resist removing step for removing the resist, and a silicon nitride film in a recess defined by the light shielding film and the hole Forming a first insulating layer by applying a transparent insulating material having a refractive index lower than that of the silicon nitride film, and flattening the first insulating layer to form a flattened film A flattening film forming step, a color filter forming step for forming a color filter on the flattening film, a second insulating layer on the color filter and forming a thin film on the second insulating layer for protection A protective film forming step of forming a film, wherein the planarizing film forming step and the protective film forming step include the first insulating layer and the second insulating film. An insulating film exposing step of exposing the edge layer to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure; and the first insulating layer and the second insulating layer exposed to the mixed gas atmosphere And an insulating film heating step for heating the substrate to a predetermined temperature.

  The solid-state imaging device manufacturing method according to claim 11, wherein a light receiving part forming step for forming a plurality of light receiving parts on the substrate for generating signal charges in response to received light, and insulation on the substrate on which the light receiving part is formed. An insulating film forming step for forming a film; a signal charge transfer portion forming step for forming a signal charge transfer portion for transferring a signal charge obtained by the plurality of light receiving portions; and a conductive light shielding on the signal charge transfer portion. A light-shielding film forming step for forming a film; and a light-transmitting electrode for forming a light-transmissive electrode made of an amorphous silicon thin film on the plurality of light-receiving portions and directly on the light-shielding film through the insulating film by a CVD method A step of forming the insulating film, wherein the insulating film forming step includes applying an insulating material on the substrate on which the light receiving portion is formed in order to form the insulating film. An insulating film exposing step of exposing the coated insulating material to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure; and the insulating material exposed to the mixed gas atmosphere at a predetermined temperature. And an insulating material heating step for heating.

  13. The method of manufacturing a thin film device according to claim 12, wherein the thin film device for CCD includes a plurality of chips having the same shape pattern formed on a substrate and an insulating thin film that is optically transparent at least on the surface. A film forming step of forming an insulating film to form the thin film, and exposing the insulating film to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure A film exposure step; a film heating step for heating the insulating film exposed to the mixed gas atmosphere to a predetermined temperature; and the heated insulating property at a predetermined inspection location in each of the plurality of chips. A film inspection step for inspecting a predetermined film with respect to a predetermined condition; and in the film inspection step, the insulating film is placed in front of the inspection portion of each chip. The thin film device if you meet a predetermined condition, characterized in that it comprises a conveying step of conveying to transfer to the next step.

  14. A program according to claim 13, which causes a computer to execute a substrate processing method, wherein the insulating film provided on the substrate is exposed to an atmosphere of a mixed gas containing ammonia and hydrogen fluoride under a predetermined pressure. It has an exposure module and an insulating film heating module for heating the insulating film exposed to the mixed gas atmosphere to a predetermined temperature.

  The program according to claim 14 is a program for causing a computer to execute a manufacturing method of a solid-state imaging device, wherein the film-thickness determining module determines a desired thickness of an insulating film provided on a substrate of the solid-state imaging device, and the insulation A pre-processing shape measurement module for measuring the shape of the film, a processing condition determination module for determining the first processing condition and the second processing condition by comparing the measured shape with the determined film thickness, An insulating film exposure module that exposes the insulating film to an atmosphere of a mixed gas containing ammonia and hydrogen fluoride under a predetermined pressure based on a first processing condition; and an insulating film exposure module that exposes the mixed gas based on the second processing condition. And an insulating film heating module for heating the insulating film exposed to the atmosphere to a predetermined temperature.

  The program according to claim 15, wherein a plurality of photoelectric conversion elements provided in a matrix on a substrate, an insulating film formed on the substrate provided with the plurality of photoelectric conversion elements, and adjacent to the photoelectric conversion elements Formed on the signal charge transfer electrode composed of a switching element and wiring, an interlayer insulating film formed on the signal charge transfer electrode, and formed on the signal charge transfer electrode via the interlayer insulating film A program for causing a computer to execute a method for manufacturing a solid-state imaging device including a light-shielding film made of a metal film, comprising: a metal film-forming module that forms the metal film to form the light-shielding film; A resist patterning module that forms a resist having a predetermined pattern for forming the light-shielding film on the formed metal film, the metal film using the resist, and the photoelectric conversion module. A patterning module that forms the light shielding film and the hole by patterning the interlayer insulating film by dry etching up to just above the element, a resist removal module that removes the resist, and a recess defined by the light shielding film and the hole A silicon nitride film forming module for forming a silicon nitride film and a transparent insulating material having a refractive index lower than that of the silicon nitride film are applied to form a first insulating layer, and the first insulating layer is planarized A flattening film forming module for forming a flattening film, a color filter forming module for forming a color filter on the flattening film, a second insulating layer on the color filter and the second insulation A protective film forming module for forming a protective film by thinning a layer, and the planarizing film forming module and the protective film forming module An insulating film exposure module for exposing the first insulating layer and the second insulating layer to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure; and exposing the first insulating layer and the second insulating layer to the mixed gas atmosphere. And an insulating film heating module for heating the first insulating layer and the second insulating layer to a predetermined temperature.

  The program according to claim 16 includes: a light receiving portion forming module that forms a plurality of light receiving portions on a substrate that generate a signal charge in response to received light; and an insulation that forms an insulating film on the substrate on which the light receiving portion is formed. A film forming module; a signal charge transfer unit forming module that forms a signal charge transfer unit that transfers signal charges obtained by the plurality of light receiving units; and a light shielding unit that forms a conductive light shielding film on the signal charge transfer unit. A film forming module; and a light transmissive electrode forming module for forming a light transmissive electrode made of an amorphous silicon thin film on the plurality of light receiving portions and directly on the light shielding film through the insulating film by a CVD method. A program for causing a computer to execute a method for manufacturing a solid-state imaging device, wherein the light-receiving unit is formed in the insulating film forming module to form the insulating film. An insulating material coating module for coating an insulating material on a substrate, an insulating film exposure module for exposing the coated insulating material to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure, and the mixed gas. And an insulating material heating module for heating the insulating material exposed to the atmosphere to a predetermined temperature.

  A program according to claim 17 is a method for manufacturing a thin film device for a CCD comprising a plurality of chips having the same shape pattern formed on a substrate and an insulating thin film that is optically transparent at least on the surface. A program to be executed, a film forming module for forming an insulating film to form the thin film, and an atmosphere of a mixed gas containing ammonia and hydrogen fluoride under a predetermined pressure. The exposed film exposure module, the film heating module that heats the insulating film exposed to the mixed gas atmosphere to a predetermined temperature, and the heating at a predetermined inspection location in each of the plurality of chips A film inspection module that performs an inspection related to a predetermined condition for an insulating film, and the film inspection module in each chip The insulating film in 査箇 plant characterized in that it comprises a transfer module for transferring the thin film device if you meet the predetermined condition to transfer to the next step.

  According to the method for manufacturing a solid-state imaging device according to claim 1 and the program according to claim 11, the insulating film on the substrate of the solid-state imaging device is exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure. The insulating film exposed to the mixed gas atmosphere is heated to a predetermined temperature. When the insulating film is exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure, a product based on the insulating film and the mixed gas is generated, and the insulating film is exposed to the mixed gas atmosphere. Is heated to a predetermined temperature, the generated product is heated and vaporized. By vaporizing this product, the upper layer of the insulating film can be removed. At this time, the production amount of the product, that is, the removal amount (film thickness) of the upper layer of the insulating film can be accurately controlled by the parameter of the mixed gas. In addition, exposure to the mixed gas and heating do not damage each element included in the substrate of the solid-state imaging element. Therefore, the removal amount of the insulating film can be accurately controlled without damaging the solid-state imaging device manufactured from the substrate. Thereby, the insulating film can be thinned.

  According to the method for manufacturing a solid-state imaging device according to claim 2, since the plasmaless etching process is performed on the substrate, in the solid-state imaging device manufactured from the substrate, charges are not accumulated in the gate electrode. Deterioration and destruction can be prevented, and energetic particles are not irradiated onto the solid-state imaging device, so that it is possible to prevent the occurrence of damaging damage (crystal defects) in the solid-state imaging device, and also due to plasma. Since an unexpected chemical reaction does not occur, the generation of impurities can be prevented, thereby preventing the processing chamber for processing the substrate from being contaminated.

  According to the method for manufacturing a solid-state imaging device according to the third aspect, it is possible to suppress a change in physical properties of the substrate surface, thereby reliably preventing a decrease in wiring reliability.

  According to the method for manufacturing a solid-state imaging device according to claim 4, the shape of the insulating film is measured, and the volume flow rate ratio of hydrogen fluoride to ammonia in the mixed gas according to the measured shape, and the predetermined pressure. Since at least one is determined, the removal amount (film thickness) of the upper layer of the insulating film can be controlled more accurately, and in addition, the efficiency of the thinning process of the insulating film can be improved.

According to the method for manufacturing a solid-state imaging device according to claim 5, the volume flow ratio of hydrogen fluoride to ammonia in the mixed gas is 1 to 1/2, and the predetermined pressure is 6.7 × 10 ⁻² to 4. Since the pressure is 0.0 Pa, the production of the product can be promoted, so that the upper layer of the insulating film can be reliably removed (thinned).

  According to the method for manufacturing a solid-state imaging device according to claim 6, since the predetermined temperature is 80 to 200 ° C., the vaporization of the product can be promoted, and thus the upper layer of the insulating film can be removed (thinned). It can be done reliably.

  According to the method for manufacturing a solid-state image pickup device according to claim 7 and the program according to claim 14, the insulating film on the substrate of the solid-state image pickup device is exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure. The insulating film exposed to the mixed gas atmosphere is heated to a predetermined temperature. When the insulating film is exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure, a product based on the insulating film and the mixed gas is generated, and the insulating film is exposed to the mixed gas atmosphere. Is heated to a predetermined temperature, the generated product is heated and vaporized. By vaporizing this product, the upper layer of the insulating film can be removed. At this time, the production amount of the product, that is, the removal amount (film thickness) of the upper layer of the insulating film can be accurately controlled by the parameter of the mixed gas. In addition, exposure to the mixed gas and heating do not damage each element included in the substrate of the solid-state imaging element. Therefore, the removal amount of the insulating film can be accurately controlled without damaging the solid-state imaging device manufactured from the substrate. Thereby, the insulating film can be thinned.

  Further, the shape of the insulating film is measured, the measured shape is compared with the determined desired film thickness, the first processing condition and the second processing condition are determined, and based on the first processing condition Since the insulating film is exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure, and the insulating film exposed to the mixed gas atmosphere is heated to a predetermined temperature based on the second processing condition, The removal amount of the insulating film can be controlled more accurately, so that the insulating film can be made thinner. In addition, the manufacturing efficiency of the solid-state imaging device can be improved.

  According to the method for manufacturing a solid-state imaging device according to claim 8, the shape of the insulating film is measured after heating the insulating film exposed to the mixed gas atmosphere to a predetermined temperature, and the measured shape is determined. Since the first processing condition and the second processing condition are changed in comparison with a desired film thickness, the removal amount of the insulating film can be controlled more accurately, and the insulating film can be further thinned. Can do.

  According to the method of manufacturing a solid-state imaging device according to claim 9, the first processing condition is at least one of a volume flow rate ratio of hydrogen fluoride to ammonia in the mixed gas and a predetermined pressure, and the second processing Since the condition is a predetermined temperature, the effects of claims 7 and 8 described above can be reliably achieved.

  According to the method for manufacturing a solid-state imaging device according to claim 10 and the program according to claim 15, the first insulating layer applied to form the planarizing film on which the color filter is formed, and the color filter The second insulating layer applied to form the protective film is exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure, and the first and second exposed to the mixed gas atmosphere. The two insulating films are heated to a predetermined temperature. When the first and second insulating films are exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure, a product based on the first and second insulating films and the mixed gas is generated. When the first and second insulating films exposed to the mixed gas atmosphere are heated to a predetermined temperature, the generated product is heated and vaporized. By vaporizing this product, the upper layers of the first and second insulating films can be removed. At this time, the production amount of the product, that is, the removal amount (film thickness) of the upper layer of the first and second insulating films can be accurately controlled by the parameters of the mixed gas. In addition, exposure to the gas mixture and heating do not damage each element of the solid-state imaging element. Therefore, the removal amount of the insulating film can be accurately controlled without damaging the solid-state imaging device. Thereby, the insulating film can be thinned.

  According to the method for manufacturing a solid-state imaging device according to claim 11 and the program according to claim 16, the insulating material applied on the substrate in order to form the insulating film on the substrate on which the light receiving unit is formed has a predetermined pressure. The insulating material exposed to the atmosphere of the mixed gas containing ammonia and hydrogen fluoride is heated to a predetermined temperature. When the insulating material is exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure, a product based on the insulating material and the mixed gas is generated, and the insulating material is exposed to the mixed gas atmosphere. Is heated to a predetermined temperature, the generated product is heated and vaporized. By vaporizing this product, the upper layer of the insulating material can be removed. At this time, the production amount of the product and the removal amount (film thickness) of the upper layer of the insulating material can be accurately controlled by the parameters of the mixed gas. In addition, exposure to the gas mixture and heating do not damage each element of the solid-state imaging element. Therefore, the removal amount of the insulating film can be accurately controlled without damaging the solid-state imaging device. Thereby, the insulating film can be thinned.

  According to the method for manufacturing a thin film device according to claim 12 and the program according to claim 17, the insulating film formed to form the thin film of the thin film device for CCD is formed with ammonia and fluorine under a predetermined pressure. The insulating film exposed to the mixed gas atmosphere containing hydrogen fluoride is heated to a predetermined temperature. When an insulating film is exposed to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure, a product based on the insulating film and the mixed gas is generated and exposed to the mixed gas atmosphere. When the formed insulating film is heated to a predetermined temperature, the generated product is heated and vaporized. By vaporizing this product, the upper layer of the insulating film can be removed. At this time, the production amount of the product and the removal amount (film thickness) of the upper layer of the insulating film can be accurately controlled by the parameters of the mixed gas. In addition, exposure to a gas mixture and heating do not damage each element of a thin film device for a CCD. Therefore, the removal amount of the insulating film can be accurately controlled without damaging each element of the thin film device. Thereby, the insulating film can be thinned. In addition, the insulating film heated at a predetermined inspection location in each of the plurality of chips is inspected with respect to a predetermined condition, and the insulating film satisfies the predetermined condition at the inspection location in each chip. In this case, since the thin film device is moved to the next step, the yield rate of CCD can be improved.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  First, a substrate processing method according to an embodiment of the present invention will be described.

  FIG. 1 is a plan view showing a schematic configuration of a substrate processing apparatus to which the substrate processing method according to the present embodiment is applied.

  In FIG. 1, a substrate processing apparatus 10 performs a reactive ion etching (hereinafter referred to as “RIE”) process on a wafer (hereinafter simply referred to as “wafer”) (substrate) W for an electronic device. A ship 11, a second process ship 12 that is arranged in parallel with the first process ship 11 and performs a COR (Chemical Oxide Removal) process and a PHT (Post Heat Treatment) process, which will be described later, on the wafer W; A loader unit 13 is provided as a rectangular common transfer chamber to which the process ship 11 and the second process ship 12 are connected.

  In addition to the first process ship 11 and the second process ship 12 described above, a FOUP (Front Opening Unified Pod) 14 as a container for containing 25 wafers W is mounted on the loader unit 13 3 Two hoop mounting tables 15, an orienter 16 that pre-aligns the position of the wafer W carried out of the hoop 14, and first and second IMS (Integrated Metrology System, Therma-Wave, Inc.) that measure the surface state of the wafer W. .) 17 and 18 are connected.

  The first process ship 11 and the second process ship 12 are connected to the side wall in the longitudinal direction of the loader unit 13 and are arranged so as to face the three hoop mounting tables 15 with the loader unit 13 interposed therebetween. Is disposed at one end in the longitudinal direction of the loader unit 13, the first IMS 17 is disposed at the other end in the longitudinal direction of the loader unit 13, and the second IMS 18 is disposed in parallel with the three hoop mounting tables 15.

  The loader unit 13 serves as a loading port for the wafer W disposed on the side wall so as to correspond to the SCARA dual arm type transport arm mechanism 19 that transports the wafer W and the FOUP mounting table 15. And three load ports 20. The transfer arm mechanism 19 takes out the wafer W from the FOUP 14 placed on the FOUP placement table 15 via the load port 20, and removes the taken wafer W from the first process ship 11, the second process ship 12, and the orienter 16. , Carry in / out to the first IMS 17 and the second IMS 18.

  The first IMS 17 is an optical system monitor, and includes a mounting table 21 on which the loaded wafer W is mounted, and an optical sensor 22 that directs the wafer W mounted on the mounting table 21. The surface shape, for example, the film thickness of the surface layer, and the CD (Critical Dimension) value of the wiring groove, gate electrode, etc. are measured. The second IMS 18 is also an optical system monitor, and has a mounting table 23 and an optical sensor 24 as in the first IMS 17, and measures the number of particles on the surface of the wafer W.

  The first process ship 11 includes a first process unit 25 as a first vacuum processing chamber that performs RIE processing on the wafer W, and a link type single pick type that delivers the wafer W to the first process unit 25. And a first load / lock unit 27 containing the first transfer arm 26.

  The first process unit 25 includes a cylindrical processing chamber container (chamber), and an upper electrode and a lower electrode disposed in the chamber, and the distance between the upper electrode and the lower electrode is RIE on the wafer W. An appropriate interval for processing is set. In addition, the lower electrode has an ESC 39 at the top for chucking the wafer W by Coulomb force or the like.

  In the first process unit 25, a processing gas is introduced into the chamber, and an electric field is generated between the upper electrode and the lower electrode, whereby the introduced processing gas is turned into plasma to generate ions and radicals. Thus, the RIE process is performed on the wafer W.

  In the first process ship 11, the internal pressure of the loader unit 13 is maintained at atmospheric pressure, while the internal pressure of the first process unit 25 is maintained at vacuum. Therefore, the first load / lock unit 27 includes a vacuum gate valve 29 at the connection portion with the first process unit 25 and an atmospheric gate valve 30 at the connection portion with the loader unit 13. It is configured as a vacuum preparatory transfer chamber that can adjust the pressure.

  Inside the first load / lock unit 27, a first transfer arm 26 is installed at a substantially central portion, and a first buffer 31 is installed on the first process unit 25 side from the first transfer arm 26. Then, the second buffer 32 is installed on the loader unit 13 side from the first transfer arm 26. The first buffer 31 and the second buffer 32 are disposed on a trajectory on which a support portion (pick) 33 that supports the wafer W disposed at the distal end portion of the first transfer arm 26 moves, and is subjected to RIE processing. By temporarily retracting the processed wafer W above the trajectory of the support portion 33, it is possible to smoothly exchange the RIE-unprocessed wafer W and the RIE-processed wafer W in the first process unit 25. .

  The second process ship 12 is connected to a second process unit 34 as a second vacuum processing chamber that performs COR processing on the wafer W, and is connected to the second process unit 34 via a vacuum gate valve 35. A third process unit 36 as a third vacuum processing chamber for performing a PHT process on the wafer W, and a link type single pick type second for delivering the wafer W to the second process unit 34 and the third process unit 36. And a second load / lock unit 49 having a built-in transfer arm 37 therein.

  2 is a cross-sectional view of the second process unit in FIG. 1, FIG. 2 (A) is a cross-sectional view along line II-II in FIG. 1, and FIG. 2 (B) is in FIG. 2 (A). It is an enlarged view of the A section.

  2A, the second process unit 34 includes a cylindrical processing chamber container (chamber) 38, an ESC 39 as a mounting table for the wafer W disposed in the chamber 38, and a chamber 38 above. As a variable butterfly valve that is arranged between the arranged shower head 40, a TMP (Turbo Molecular Pump) 41 that exhausts gas in the chamber 38, and the chamber 38 and the TMP 41, and controls the pressure in the chamber 38. And an APC (Automatic Pressure Control) valve 42.

  The ESC 39 has an electrode plate (not shown) to which a DC voltage is applied, and adsorbs and holds the wafer W by a Coulomb force or a Johnson-Rahbek force generated by the DC voltage. The ESC 39 has a refrigerant chamber (not shown) as a temperature control mechanism. A coolant having a predetermined temperature, for example, cooling water or a Galden solution, is circulated and supplied to the coolant chamber, and the processing temperature of the wafer W adsorbed and held on the upper surface of the ESC 39 is controlled by the temperature of the coolant. Further, the ESC 39 has a heat transfer gas supply system (not shown) that uniformly supplies heat transfer gas (helium gas) between the upper surface of the ESC 39 and the back surface of the wafer W. During the COR process, the heat transfer gas exchanges heat between the ESC 39 maintained at a desired designated temperature by the refrigerant and the wafer W, thereby cooling the wafer W efficiently and uniformly.

  The ESC 39 has a plurality of pusher pins 56 as lift pins that can protrude from the upper surface thereof. These pusher pins 56 are accommodated in the ESC 39 and subjected to COR processing when the wafer W is sucked and held by the ESC 39. When the wafer W is unloaded from the chamber 38, it protrudes from the upper surface of the ESC 39 and lifts the wafer W upward.

  The shower head 40 has a two-layer structure, and has a first buffer chamber 45 and a second buffer chamber 46 in each of the lower layer portion 43 and the upper layer portion 44. The first buffer chamber 45 and the second buffer chamber 46 communicate with the chamber 38 through gas vents 47 and 48, respectively. That is, the shower head 40 has two plate-like bodies (lower layers) stacked in a layered manner having internal passages into the gas chambers 38 for the gases supplied to the first buffer chamber 45 and the second buffer chamber 46, respectively. Part 43 and upper layer part 44).

When the COR process is performed on the wafer W, NH ₃ (ammonia) gas is supplied to the first buffer chamber 45 from an ammonia gas supply pipe 57 described later, and the supplied ammonia gas is supplied to the chamber through the gas vent 47. 38, and HF (hydrogen fluoride) gas is supplied to the second buffer chamber 46 from a hydrogen fluoride gas supply pipe 58, which will be described later, and the supplied hydrogen fluoride gas is supplied to the gas vent hole 48. Is supplied into the chamber 38 via

  The shower head 40 incorporates a heater (not shown), for example, a heating element. This heating element is preferably disposed on the upper layer portion 44 to control the temperature of the hydrogen fluoride gas in the second buffer chamber 46.

  In addition, as shown in FIG. 2B, the openings into the chamber 38 in the gas vent holes 47 and 48 are formed so as to expand toward the end. Thereby, ammonia gas or hydrogen fluoride gas can be efficiently diffused into the chamber 38. Further, since the gas vent holes 47 and 48 have a constricted cross section, the deposits generated in the chamber 38 are directed to the gas vent holes 47 and 48, and then to the first buffer chamber 45 and the second buffer chamber 46. Backflow can be prevented. The gas vents 47 and 48 may be spiral vents.

  The second process unit 34 performs COR processing on the wafer W by adjusting the pressure in the chamber 38 and the volume flow ratio of ammonia gas and hydrogen fluoride gas. Further, since the second process unit 34 is designed so that ammonia gas and hydrogen fluoride gas are mixed for the first time in the chamber 38 (postmix design), the above two kinds of gases are introduced into the chamber 38. Until then, the two gases are prevented from mixing and the hydrogen fluoride gas and ammonia gas are prevented from reacting before being introduced into the chamber 38.

  In the second process unit 34, the side wall of the chamber 38 incorporates a heater (not shown), for example, a heating element, and prevents the ambient temperature in the chamber 38 from being lowered. Thereby, the reproducibility of the COR processing can be improved. Further, the heating element in the side wall prevents the by-product generated in the chamber 38 from adhering to the inside of the side wall by controlling the temperature of the side wall.

  Returning to FIG. 1, the third process unit 36 includes a housing-like processing chamber container (chamber) 50, a stage heater 51 as a mounting table for the wafer W disposed in the chamber 50, and the stage heater 51. And a buffer arm 52 that lifts the wafer W placed on the stage heater 51 upward, and a PHT chamber lid (not shown) as an openable / closable lid that shuts off the inside and outside atmosphere of the chamber.

  The stage heater 51 is made of aluminum having an oxide film formed on the surface, and heats the wafer W placed by a built-in heating wire or the like to a predetermined temperature. Specifically, the stage heater 51 directly heats the placed wafer W to 100 to 200 ° C., preferably about 135 ° C., for at least 1 minute.

  The PHT chamber lid is provided with a silicon rubber seat heater. A cartridge heater (not shown) is built in the side wall of the chamber 50, and the cartridge heater controls the wall surface temperature of the side wall of the chamber 50 to 25 to 80 ° C. This prevents by-products from adhering to the side walls of the chamber 50, prevents generation of particles due to the attached by-products, and extends the cleaning cycle of the chamber 50. The outer periphery of the chamber 50 is covered with a heat shield.

  As a heater for heating the wafer W from above, an ultraviolet radiation (UV radiation) heater may be provided instead of the above-described sheet heater. Examples of the ultraviolet radiation heater include an ultraviolet lamp that emits ultraviolet light having a wavelength of 190 to 400 nm.

  The buffer arm 52 temporarily retracts the wafer W on which the COR processing has been performed above the trajectory of the support portion 53 in the second transfer arm 37, whereby the second process unit 34 and the third process unit 36. The wafer W can be smoothly exchanged.

  The third process unit 36 performs a PHT process on the wafer W by adjusting the temperature of the wafer W.

  The second load / lock unit 49 includes a housing-like transfer chamber (chamber) 70 in which the second transfer arm 37 is built. The internal pressure of the loader unit 13 is maintained at atmospheric pressure, while the internal pressures of the second process unit 34 and the third process unit 36 are maintained at vacuum. Therefore, the second load / lock unit 49 includes the vacuum gate valve 54 at the connection portion with the third process unit 36 and the atmospheric door valve 55 at the connection portion with the loader unit 13. It is configured as a vacuum preliminary transfer chamber that can be adjusted.

  FIG. 3 is a perspective view showing a schematic configuration of the second process ship in FIG.

  In FIG. 3, the second process unit 34 includes an ammonia gas supply pipe 57 that supplies ammonia gas to the first buffer chamber 45 and a hydrogen fluoride gas supply that supplies hydrogen fluoride gas to the second buffer chamber 46. A pipe 58, a pressure gauge 59 for measuring the pressure in the chamber 38, and a chiller unit 60 for supplying a refrigerant to a cooling system disposed in the ESC 39 are provided.

  The ammonia gas supply pipe 57 is provided with an MFC (Mass Flow Controller) (not shown). The MFC adjusts the flow rate of the ammonia gas supplied to the first buffer chamber 45 and is connected to the hydrogen fluoride gas supply pipe 58. MFC (not shown) is also provided, and the MFC adjusts the flow rate of the hydrogen fluoride gas supplied to the second buffer chamber 46. The MFC of the ammonia gas supply pipe 57 and the MFC of the hydrogen fluoride gas supply pipe 58 cooperate to adjust the volume flow ratio of the ammonia gas and the hydrogen fluoride gas supplied to the chamber 38.

  A second process unit exhaust system 61 connected to a DP (Dry Pump) (not shown) is disposed below the second process unit 34. The second process unit exhaust system 61 includes an exhaust pipe 63 communicating with an exhaust duct 62 disposed between the chamber 38 and the APC valve 42, and an exhaust pipe 64 connected to the lower side (exhaust side) of the TMP 41. And exhausts the gas and the like in the chamber 38. The exhaust pipe 64 is connected to the exhaust pipe 63 before the DP.

The third process unit 36 exhausts the nitrogen gas supply pipe 65 that supplies nitrogen (N ₂ ) gas to the chamber 50, the pressure gauge 66 that measures the pressure in the chamber 50, the nitrogen gas in the chamber 50, and the like. And a third process unit exhaust system 67.

  The nitrogen gas supply pipe 65 is provided with an MFC (not shown), and the MFC adjusts the flow rate of the nitrogen gas supplied to the chamber 50. The third process unit exhaust system 67 includes a main exhaust pipe 68 communicating with the chamber 50 and connected to the DP, an APC valve 69 disposed in the middle of the main exhaust pipe 68, and the main exhaust pipe 68 to the APC valve. And a sub-exhaust pipe 68a that branches to avoid 69 and is connected to the main exhaust pipe 68 before the DP. The APC valve 69 controls the pressure in the chamber 50.

  The second load / lock unit 49 includes a nitrogen gas supply pipe 71 that supplies nitrogen gas to the chamber 70, a pressure gauge 72 that measures the pressure in the chamber 70, and a second gas that exhausts nitrogen gas and the like in the chamber 70. The load / lock unit exhaust system 73 and an atmosphere communication pipe 74 that opens the inside of the chamber 70 to the atmosphere.

  The nitrogen gas supply pipe 71 is provided with an MFC (not shown), and the MFC adjusts the flow rate of nitrogen gas supplied to the chamber 70. The second load / lock unit exhaust system 73 comprises one exhaust pipe, which communicates with the chamber 70 and is connected to the main exhaust pipe 68 in the third process unit exhaust system 67 before the DP. The The second load / lock unit exhaust system 73 and the atmosphere communication pipe 74 have an exhaust valve 75 and a relief valve 76 that can be opened and closed, respectively, and the exhaust valve 75 and the relief valve 76 cooperate with each other in the chamber 70. The pressure is adjusted from atmospheric pressure to any desired degree of vacuum.

  FIG. 4 is a diagram showing a schematic configuration of a unit driving dry air supply system of the second load / lock unit in FIG. 3.

In FIG. 4, the dry air supply destination of the unit drive dry air supply system 77 of the second load / lock unit 49 includes a door valve cylinder for driving the slide door of the atmospheric door valve 55, and nitrogen gas supply as the N ₂ purge unit. The MFC included in the pipe 71, the relief valve 76 included in the atmosphere communication pipe 74 serving as a relief unit for opening to the atmosphere, the exhaust valve 75 included in the second load / lock unit exhaust system 73 serving as the evacuation unit, and the vacuum gate valve 54 Corresponds to a gate valve cylinder for driving a slide gate.

  The unit driving dry air supply system 77 includes a sub dry air supply pipe 79 branched from the main dry air supply pipe 78 included in the second process ship 12, a first solenoid valve 80 connected to the sub dry air supply pipe 79, and A second solenoid valve 81.

  The first solenoid valve 80 is connected to the door valve cylinder, the MFC, the relief valve 76, and the gate valve cylinder via each of the dry air supply pipes 82, 83, 84, 85, and controls the amount of dry air supplied thereto. Thus, the operation of each part is controlled. The second solenoid valve 81 is connected to the exhaust valve 75 via a dry air supply pipe 86 and controls the operation of the exhaust valve 75 by controlling the amount of dry air supplied to the exhaust valve 75.

The MFC in the nitrogen gas supply pipe 71 is also connected to a nitrogen (N ₂ ) gas supply system 87.

  The second process unit 34 and the third process unit 36 also include a unit drive dry air supply system having the same configuration as the unit drive dry air supply system 77 of the second load / lock unit 49 described above.

  Returning to FIG. 1, the substrate processing apparatus 10 includes a system controller that controls the operations of the first process ship 11, the second process ship 12, and the loader unit 13, and an operation arranged at one end in the longitudinal direction of the loader unit 13. And a controller 88.

  The operation controller 88 has a display unit composed of, for example, an LCD (Liquid Crystal Display), and the display unit displays the operation status of each component of the substrate processing apparatus 10.

  As shown in FIG. 5, the system controller includes an EC (Equipment Controller) 89, three MCs (Module Controllers) 90, 91, and 92, and a switching hub 93 that connects the EC 89 and each MC. The system controller is connected from the EC 89 via a LAN (Local Area Network) 170 to a PC 171 as a MES (Manufacturing Execution System) that manages the manufacturing process of the entire factory where the substrate processing apparatus 10 is installed. The MES cooperates with the system controller to feed back real-time information relating to processes in the factory to a core business system (not shown) and makes a determination relating to the process in consideration of the load of the entire factory.

  The EC 89 is a main control unit (master control unit) that controls each operation of the substrate processing apparatus 10 by controlling each MC. The EC 89 includes a CPU, a RAM, an HDD, and the like, and the CPU sends a control signal to each MC in accordance with the processing method of the wafer W designated by the user or the like in the operation controller 88, that is, a program corresponding to the recipe. By transmitting, the operations of the first process ship 11, the second process ship 12, and the loader unit 13 are controlled.

  The switching hub 93 switches the MC as a connection destination of the EC 89 in accordance with a control signal from the EC 89.

  MCs 90, 91, and 92 are sub-control units (slave control units) that control the operations of the first process ship 11, the second process ship 12, and the loader unit 13, respectively. Each MC is connected to each I / O (input / output) module 97, 98, 99 via a GHOST network 95 by a DIST (Distribution) board 96. The GHOST network 95 is a network realized by an LSI called GHOST (General High-Speed Optimum Scalable Transceiver) mounted on an MC board included in the MC. A maximum of 31 I / O modules can be connected to the GHOST network 95. In the GHOST network 95, the MC corresponds to the master and the I / O module corresponds to the slave.

  The I / O module 98 includes a plurality of I / O units 100 connected to each component (hereinafter referred to as “end device”) in the second process ship 12, and includes a control signal and each of the end devices. Transmits output signals from end devices. Examples of the end device connected to the I / O unit 100 in the I / O module 98 include an MFC of the ammonia gas supply pipe 57, an MFC of the hydrogen fluoride gas supply pipe 58, and a pressure gauge 59 in the second process unit 34. And the APC valve 42, the MFC of the nitrogen gas supply pipe 65 in the third process unit 36, the pressure gauge 66, the APC valve 69, the buffer arm 52 and the stage heater 51, and the nitrogen gas supply pipe 71 in the second load / lock unit 49. And the first solenoid valve 80 and the second solenoid valve 81 in the unit driving dry air supply system 77.

  The I / O modules 97 and 99 have the same configuration as the I / O module 98 and correspond to the connection relationship between the MC 90 and the I / O module 97 corresponding to the first process ship 11 and the loader unit 13. Since the connection relationship between the MC 92 and the I / O module 99 is the same as the connection relationship between the MC 91 and the I / O module 98 described above, description thereof will be omitted.

  Each GHOST network 95 is also connected to an I / O board (not shown) that controls input / output of digital signals, analog signals, and serial signals in the I / O unit 100.

  When the COR processing is performed on the wafer W in the substrate processing apparatus 10, the CPU of the EC 89 performs I / O in the switching hub 93, MC 91, GHOST network 95, and I / O module 98 in accordance with a program corresponding to the recipe of the COR processing. The COR process is executed in the second process unit 34 by transmitting a control signal to a desired end device via the / O unit 100.

  Specifically, the CPU sends a control signal to the MFC of the ammonia gas supply pipe 57 and the MFC of the hydrogen fluoride gas supply pipe 58 to thereby set the volume flow rate ratio of ammonia gas and hydrogen fluoride gas in the chamber 38 to a desired value. The pressure in the chamber 38 is adjusted to a desired value by adjusting the value and sending a control signal to the TMP 41 and the APC valve 42. Further, at this time, the pressure gauge 59 transmits the pressure value in the chamber 38 as an output signal to the CPU of the EC 89, and the CPU, based on the transmitted pressure value in the chamber 38, the MFC of the ammonia gas supply pipe 57, Control parameters of the MFC, APC valve 42 and TMP 41 of the hydrogen fluoride gas supply pipe 58 are determined.

  When performing the PHT process on the wafer W, the CPU of the EC 89 transmits a control signal to a desired end device in accordance with a program corresponding to the recipe of the PHT process, so that the third process unit 36 performs the PHT process. Execute.

  Specifically, the CPU adjusts the pressure in the chamber 50 to a desired value by transmitting a control signal to the MFC and APC valve 69 of the nitrogen gas supply pipe 65, and transmits the control signal to the stage heater 51. Thus, the temperature of the wafer W is adjusted to a desired temperature. At this time, the pressure gauge 66 transmits the pressure value in the chamber 50 as an output signal to the CPU of the EC 89, and the CPU, based on the transmitted pressure value in the chamber 50, the APC valve 69 and the nitrogen gas supply pipe. 65 control parameters of MFC are determined.

  In the system controller of FIG. 5, the plurality of end devices are not directly connected to the EC 89, but the I / O unit 100 connected to the plurality of end devices is modularized to form an I / O module. Since the / O module is connected to the EC 89 via the MC and the switching hub 93, the communication system can be simplified.

  Further, the control signal transmitted by the CPU of the EC 89 includes the address of the I / O unit 100 connected to the desired end device and the address of the I / O module including the I / O unit 100. The switching hub 93 refers to the address of the I / O module in the control signal, and the GHOST of the MC refers to the address of the I / O unit 100 in the control signal, so that the switching hub 93 and the MC transmit the control signal to the CPU. It is possible to eliminate the necessity of making the previous inquiry, thereby realizing smooth transmission of the control signal.

By the way, as described above, in order to improve the light condensing property of the solid-state imaging device, it is necessary to reduce the thickness of the insulating film (SiO ₂ film) in order to improve the positional accuracy during manufacturing. . In addition, it is necessary to prevent the solid-state imaging device from being damaged when the insulating film is thinned.

  Correspondingly, the substrate processing method according to the present embodiment performs COR processing and PHT processing on the wafer W in order to reduce the thickness of the insulating film without damaging the solid-state imaging device.

  The COR process is a process of generating a product by chemically reacting the oxide film of the object to be processed and gas molecules, and the PHT process is a chemical reaction of the COR process by heating the object to be processed by the COR process. In this process, the product generated on the object to be processed is vaporized and thermally oxidized (Thermal Oxidation) and removed from the object to be processed. As described above, since the COR process and the PHT process, in particular, the COR process is a process for removing the oxide film of the object to be processed without using plasma and without using a water component, the plasmaless etching process and the dry cleaning process are performed. Corresponds to (dry cleaning treatment).

In the substrate processing method according to the present embodiment, ammonia gas and hydrogen fluoride gas are used as gases. Here, hydrogen fluoride gas promotes corrosion of the SiO ₂ layer, and ammonia gas restricts the reaction between the oxide film and hydrogen fluoride gas as necessary, and finally generates a reaction by-product for stopping the reaction. Synthesize a product (By-product). Specifically, by using the following chemical reaction in the COR process and the PHT process, the upper layer of the insulating film made of SiO ₂ is removed to make the insulating film have a desired film thickness.
(COR processing)
SiO ₂ + 4HF → SiF ₄ + 2H ₂ O ↑
SiF ₄ + 2NH ₃ + 2HF → (NH ₄ ) ₂ SiF ₆
(PHT treatment)
(NH ₄ ) ₂ SiF ₆ → SiF ₄ ↑ + 2NH ₃ ↑ + 2HF ↑
The present inventors have confirmed that the COR treatment and PHT treatment using the chemical reaction described above have the following characteristics. In the PHT process, a small amount of N ₂ and H ₂ is also generated.
1) The thermal oxide film selectivity (removal rate) is high.

Specifically, in the COR process and the PHT process, the selectivity of the thermal oxide film is high while the selectivity of polysilicon is low. Therefore, it is possible to efficiently remove the pseudo-SiO ₂ layer having properties similar to those of the surface layer and the SiO ₂ film of the insulating film made of SiO ₂ film is a thermal oxide film. This pseudo SiO ₂ layer is also referred to as “altered layer” or “sacrificial layer”.
2) The growth rate of the natural oxide film on the surface of the insulating film from which the surface layer and the like have been removed is slow.

Specifically, on the surface of the insulating film from which the upper layer was removed by wet etching, the growth time of a natural oxide film having a thickness of 3 mm was 10 minutes, whereas the upper layer was removed by COR processing and PHT processing. On the surface of the insulating film, the growth time of the natural oxide film having a thickness of 3 mm is 2 hours or more. Therefore, an unnecessary oxide film is not generated in the manufacturing process of the electronic device, and the reliability of the electronic device can be improved.
3) The reaction proceeds in a dry environment.

Specifically, water is not used for the reaction in the COR process, and water generated by the COR process is vaporized by the PHT process, so that an OH group is arranged on the surface of the insulating film from which the upper layer is removed. There is nothing. Therefore, the surface of the insulating film does not become hydrophilic, and the surface does not absorb moisture, so that it is possible to prevent a reduction in wiring reliability of the electronic device.
4) The amount of product produced is saturated after a predetermined time.

Specifically, when a predetermined time elapses, the amount of product generated does not increase even if the insulating layer is continuously exposed to a mixed gas of ammonia gas and hydrogen fluoride gas thereafter. The amount of product generated is determined by parameters of the mixed gas such as the partial pressure of the mixed gas and volume flow rate ratio, and parameters such as the pressure in the chamber 38 and the heating temperature of the stage heater 51. Therefore, the removal amount of the insulating film can be controlled accurately and easily.
5) Very few particles are generated.

  Specifically, in the second process unit 34 and the third process unit 36, even if the upper layer of the insulating film on the 2000 wafers W is removed, particles adhere to the inner walls of the chamber 38 and the chamber 50. Is hardly observed. Therefore, there is no short circuit of wiring via particles in the electronic device, and the reliability of the electronic device can be improved.

  Next, a substrate processing method according to this embodiment will be described.

In this process, a process of etching the insulating film formed of SiO ₂ to a desired thickness is performed in the manufacturing process of the electronic device. Specifically, in a manufacturing process of a CCD sensor as an electronic device, a process of etching a planarizing film on which a color filter is formed and a protective film of the color filter to a desired film thickness is performed.

  FIG. 6 is a diagram showing a schematic configuration of a CCD sensor to which the substrate processing method according to the present embodiment is applied, and FIG. 6A is a diagram for explaining elements on the wafer W in the CCD sensor. FIG. 6B is a partial cross-sectional view of the CCD sensor.

  As shown in FIG. 6A, the CCD sensor 200 includes a wafer W, a photoelectric conversion element (chip) 210 as a plurality of light receiving portions provided in a matrix on the wafer W, and a diagram of the photoelectric conversion element 210. A plurality of vertical transfer register units 220 provided along each column in the middle vertical direction, and a horizontal transfer provided along a column in the horizontal direction in the figure of the photoelectric conversion element 210 in the upper part of the vertical transfer register unit 220 in the figure. A register unit 230 and an output unit 240 connected to the horizontal transfer register unit 230 are provided.

  The photoelectric conversion element 210 has a photodiode configuration, for example, and converts light incident from the light receiving surface into a signal charge corresponding to the amount of light. The vertical transfer register unit 220 includes a switching element and a wiring (not shown), receives the signal charge accumulated in each photoelectric conversion element 210 via a reading gate part (not shown), and transfers it in the vertical direction. The horizontal transfer register unit 230 transfers the signal charges received from the vertical transfer register unit 220 in the horizontal direction and transmits them to the output unit 240. The output unit 240 outputs the signal charge received from the horizontal transfer register unit 230 as an image signal.

Further, as shown in FIG. 6B, an insulating film 251 made of a SiO ₂ oxide film is formed on the wafer W, and the vertical transfer register unit 220 has transfer electrodes (on the insulating film 251). A signal charge transfer unit) 221 and a light shielding film 223 made of a metal such as aluminum and formed to cover the transfer electrode 221 with the interlayer insulating film 222 interposed therebetween. The CCD sensor 200 covers a silicon nitride film 252 as a protective film made of Si ₃ N ₄ formed on the wafer W so as to cover the photoelectric conversion element 210 and the vertical transfer register unit 220, and the silicon nitride film 252. A planarizing film 253 made of an insulating material (SiO ₂ ) having a refractive index lower than that of the silicon nitride film 252 having a planarized upper surface and a green color filter 255 formed on the planarizing film 253, A color filter 254 including a red color filter 256 and a blue color filter 257; a protective film 258 formed of an insulating material (SiO ₂ ) formed on the color filter 254; and a microlens 259 formed on the protective film 258. Is provided.

  FIG. 7 is a diagram showing a substrate processing method according to the present embodiment.

  Hereinafter, a case where this process is executed to form the planarizing film 253 in the CCD sensor 200 shown in FIG. 6 will be described. This process is also performed when the protective film 258 is formed, but the process is the same as that when the planarizing film 253 is formed, and a description thereof will be omitted.

  First, prior to this process, an insulating film 251 is formed on the wafer W on which the photoelectric conversion elements 210 are formed in a matrix, and a conductive film made of a conductive material such as polysilicon or amorphous silicon is formed. In order to form the transfer electrode 221, a photoresist layer is formed in a predetermined pattern. Next, using this photoresist layer as a mask, the conductive film is etched by RIE processing to form the transfer electrode 221.

Next, an insulating film is formed to form the interlayer insulating film 222, and the insulating film is similarly etched by RIE processing using the photoresist layer as a mask to form the interlayer insulating film 222. Next, a conductive metal film is formed to form the light-shielding film 223, and the insulating film 251 is etched by RIE processing to the vicinity immediately above the metal film and the photoelectric conversion element 210 using the photoresist layer as a mask. Then, the light shielding film 223 and the hole 251a are formed. Then, a silicon nitride film 252 made of Si ₃ N ₄ is formed on the entire surface, and an insulating film 261 made of SiO _{2 having} a predetermined thickness is formed on the entire surface (see FIG. 7A). The insulating film 261 is formed to be thicker than the desired thickness of the planarization film 253 so that the planarization film 253 having a desired thickness is formed by the processing of this substrate.

First, the wafer W (see FIG. 7A) on which the insulating film 261 is formed in order to form the planarizing film 253 having the desired thickness described above is accommodated in the chamber 38 of the second process unit 34, and The pressure in the chamber 38 is adjusted to a predetermined pressure, and ammonia gas, hydrogen fluoride gas, and argon (Ar) gas as a dilution gas are introduced into the chamber 38, and the inside of the chamber 38 is a mixed gas atmosphere. The insulating film 261 is exposed to a mixed gas atmosphere under a predetermined pressure (insulating film exposing step) (see FIG. 7B). As a result, SiO ₂ forming the insulating film 261 generates a product having a complex structure from ammonia gas and hydrogen fluoride gas, and changes the upper layer of the insulating film 261 into a product layer 262 made of the product (FIG. 7 (C)).

Next, the wafer W on which the product layer 262 is formed is placed on the stage heater 51 in the chamber 50 of the third process unit 36, and the pressure in the chamber 50 is adjusted to a predetermined pressure. Nitrogen gas is introduced to generate a viscous flow, and the wafer W is heated to a predetermined temperature by the stage heater 51 (insulating film heating step). At this time, the complex structure of the product in the product layer 262 is decomposed by heat, and the product is vaporized by being separated into silicon tetrafluoride (SiF ₄ ), ammonia, and hydrogen fluoride (see FIG. 7D). . These vaporized molecules are entrained in the viscous flow and exhausted from the chamber 50 by the third process unit exhaust system 67. Accordingly, the upper layer of the insulating film 261 is removed, and a planarization film 253 having a desired thickness is formed (see FIG. 7E).

  In the above process, the thickness of the planarization film 253 to be formed is determined by the thickness of the product layer 262. The amount of product produced is determined by the parameters of the mixed gas, such as the partial pressure of the mixed gas of ammonia gas and hydrogen fluoride gas, the volume flow ratio of the hydrogen fluoride gas to ammonia gas, the pressure in the chamber 38 and the stage heater 51. It is determined by parameters such as the heating temperature of the placed wafer W. For this reason, the thickness of the product layer 262 can be easily adjusted by controlling the above-described parameters of the mixed gas. Therefore, the planarization film 253 can be accurately formed in a desired thickness by controlling the parameters of the mixed gas such as the pressure of the mixed gas and the volume flow rate ratio. Thereby, in the CCD sensor 200, the planarization film 253 can be thinned.

  A method for adjusting the thickness of the product layer 262, that is, a method for controlling the thickness of the planarizing film 253 will be described in detail. First, before the COR processing is performed on the wafer W, the surface shape of the insulating film 261, for example, the CD value of the film thickness is measured (pre-processing shape measurement step). Next, the CPU of the EC 89 compares the measured value of the surface shape with the desired film thickness of the planarization film 253 set in advance, and compares the surface shape of the insulating film 261 and the desired film thickness of the planarization film 253. The COR processing condition parameter (first processing condition) and the PHT processing condition parameter (second processing condition) are determined based on the removal amount data indicating the relationship between the removal amount of the upper layer of the insulating film 261 and the film thickness to be (Processing condition determination step). The above-described removal amount data is set in advance by experiments, for example, and the removal amount data and data on the desired film thickness of the planarization film 253 are stored in advance in the storage unit of the EC 89. As described above, the COR processing condition parameters include the mixed gas parameters such as the partial pressure of the mixed gas of ammonia gas and hydrogen fluoride gas, the volume flow ratio of the hydrogen fluoride gas to ammonia gas, and the pressure in the chamber 38. The PHT processing condition parameters include the heating temperature of the wafer W placed on the stage heater 51 and the like. Accordingly, the removal amount of the upper layer of the insulating film 261 (the growth amount of the film thickness of the product layer 262) can be accurately controlled, and therefore the planarization film 253 can be accurately formed to a desired thickness. Thus, the planarization film 253 can be thinned. Further, the efficiency of thinning the planarizing film 253 can be improved.

  Next, the surface shape of the edge film 261 after COR processing and PHT processing is measured (post-processing shape measurement step). The CPU of the EC 89 compares the measured value of the measured surface shape with the desired film thickness of the planarization film 253, and based on the removal amount data described above, the COR processing condition parameter and the PHT determined as described above. The processing condition parameter is changed (processing condition changing step). As a result, the amount of removal of the upper layer of the insulating film 261 can be controlled more accurately. Therefore, the planarizing film 253 can be more accurately formed to a desired thickness, and the planarizing film 253 can be made thinner. Can be Further, the efficiency of thinning the planarizing film 253 can be further improved.

  In addition, before the COR process is performed on the wafer W, the surface shape of the insulating film 261, for example, the CD value of the film thickness is measured, and the CPU of the EC 89 performs the insulating film 261 in accordance with the measured value of the surface shape. It is also preferable to determine the value of the process condition parameter in the COR process or PHT process based on a predetermined relationship between the surface shape of the process and the process condition parameter related to the removal amount of the upper layer of the insulating film 261. Accordingly, the removal amount of the upper layer of the insulating film 261 (the growth amount of the film thickness of the product layer 262) can be accurately controlled, and therefore the planarization film 253 can be accurately formed to a desired thickness. The planarizing film 25 can be made thinner. Further, the efficiency of thinning the planarizing film 253 can be improved.

  The predetermined relationship is the difference in the surface shape of the insulating film 261 before and after performing the COR process and the PHT process measured by the first IMS 17 in the initial stage of a lot for processing a plurality of wafers W. It is set based on the removal amount of the upper layer of the insulating film 261 by the COR process and the PHT process and the process condition parameters in the COR process and the PHT process at this time. The processing condition parameters include the pressure of the mixed gas of ammonia gas and hydrogen fluoride gas, the volume flow rate ratio of hydrogen fluoride gas to ammonia gas, the predetermined pressure in the chamber 38 and the stage heater 51 as described above. This corresponds to the heating temperature of the wafer W thus formed. The predetermined relationship set in this way is stored in the HDD or the like of the EC 89, and is referred to as the processing condition parameter as described above in the processing of the wafer W after the initial lot.

  Further, based on the difference in the surface shape of the insulating film 261 before and after the COR processing and PHT processing of a certain wafer W, it is determined whether or not to perform the COR processing and PHT processing on the wafer W again. Further, when the COR process and the PHT process are performed again, the CPU of the EC 89 performs the predetermined process according to the surface shape of the insulating film 261 after the COR process and the PHT process of the wafer W are performed. You may determine the condition parameter of COR processing and PHT processing based on a relationship.

  Furthermore, the surface shape of the insulating film 261 after performing the COR process and the PHT process measured by the first IMS 17 is measured at measurement points set in advance in each of the photoelectric conversion elements 210, and is measured at all measurement points. Only when the insulating film 261 is removed to a desired thickness, the wafer W may be transported to move to the next process. Thereby, the yield rate of the CCD sensor 200 can be improved.

In the second process unit 34, since the hydrogen fluoride gas easily reacts with moisture, it is preferable to set the volume of ammonia gas in the chamber 38 to be larger than the volume of the hydrogen fluoride gas. It is preferable to remove as much as possible. Specifically, the volume flow rate (SCCM) ratio of hydrogen fluoride gas to ammonia gas in the mixed gas in the chamber 38 is preferably 1 to 1/2, and the predetermined pressure in the chamber 38 is 6. The pressure is preferably 7 × 10 ^{−2 to} 4.0 Pa (0.5 to 30 mTorr). Thereby, since the flow ratio of the mixed gas in the chamber 38 is stabilized, the production of the product can be promoted.

Further, when the predetermined pressure in the chamber 38 is 6.7 × 10 ^{−2 to} 4.0 Pa (0.5 to 30 mTorr), the amount of product produced can be reliably saturated after a predetermined time has elapsed, Thereby, the etching depth (removal amount) can be reliably controlled (self-limited). For example, when the predetermined pressure in the chamber 38 is 1.3 Pa (10 mTorr), the progress of etching stops after about 3 minutes from the start of the COR process. The etching depth at this time is about 15 nm. When the predetermined pressure in the chamber 38 is 2.7 Pa (20 mTorr), the progress of etching stops after about 3 minutes from the start of the COR process. The etching depth at this time is approximately 24 nm.

  In addition, since the reaction of the reactant is promoted near normal temperature, the temperature of the ESC 39 on which the wafer W is placed is preferably set to 25 ° C. by a built-in temperature control mechanism (not shown). Furthermore, since the by-product generated in the chamber 38 is less likely to adhere as the temperature is higher, the inner wall temperature in the chamber 38 is preferably set to 50 ° C. by a heater (not shown) embedded in the side wall. .

In the third process unit 36, the reactant is a complex compound containing a coordination bond, and the complex compound has a weak binding force and promotes thermal decomposition even at a relatively low temperature. Is preferably 80 to 200 ° C., and the time for performing the PHT treatment on the wafer W is preferably 60 to 180 seconds. In order to generate a viscous flow in the chamber 50, it is not preferable to increase the degree of vacuum in the chamber 50, and a gas flow with a constant flow rate is required. Accordingly, the predetermined pressure in the chamber 50 is preferably 6.7 × 10 to 1.3 × 10 ² Pa (500 mTorr to 1 Torr), and the flow rate of nitrogen gas is preferably 500 to 3000 SCCM. Thereby, since a viscous flow can be reliably generated in the chamber 50, gas molecules generated by thermal decomposition of the product can be reliably removed.

  The wafer W on which the planarization film 253 is formed by this process is then formed with the color filter 254, the protective film 258 is formed by this process in the same manner as the formation of the planarization film 253, and the microlens 259 is formed. The CCD sensor 200 is formed.

As described above, according to the substrate processing method of the present embodiment, the wafer on which the insulating film 261 having a predetermined thickness made of SiO ₂ is formed in order to form the planarizing film 253 having a desired thickness. W is exposed to a mixed gas atmosphere composed of ammonia gas, hydrogen fluoride gas, and argon gas under a predetermined pressure, and the wafer W exposed to the mixed gas atmosphere is heated to a predetermined temperature. As a result, a product having a complex structure is generated from SiO ₂ , ammonia gas, and hydrogen fluoride gas forming the insulating film 261, and a product layer 262 having a desired thickness is generated. In the produced product, the complex structure of the product is decomposed by heat, and the product is vaporized by being separated into silicon tetrafluoride, ammonia and hydrogen fluoride. By the vaporization of the product, the product layer 263 which is an upper layer of the insulating film 261 can be removed, and the planarization film 253 having a desired thickness can be formed.

  At this time, the production amount of the product, that is, the thickness of the product layer 262 is a parameter of the mixed gas such as the pressure of the mixed gas of ammonia gas and hydrogen fluoride gas and the volume flow ratio of the hydrogen fluoride gas to the ammonia gas. The pressure can be controlled by parameters such as the pressure in the chamber 38 and the heating temperature of the wafer W placed on the stage heater 51. Therefore, it is possible to accurately control the thickness of the product layer 262 generated by controlling the parameters such as the gas mixture, and it is possible to accurately control the removal amount of the insulating film 261. Thereby, the planarization film 253 can be accurately formed to a desired thickness by such isotropic etching, and the planarization film 253 can be thinned. For this reason, the light condensing property of the CCD sensor 200 can be improved and the sensitivity of the photoelectric conversion element 210 can be improved, and the upper layer components can be accurately aligned with the underlying device in the manufacture of the CCD sensor 200. it can.

  In addition, since the amount of product generated is saturated after a predetermined time has elapsed, the insulating film 261 is not completely removed in this process. Therefore, it is possible to prevent a decrease in wiring reliability of a CCD sensor manufactured from the wafer W.

  Further, according to the substrate processing method of the present embodiment, the wafer W is subjected to the plasmaless etching process and the upper layer of the insulating film 261 is removed. Therefore, in the CCD sensor 200 manufactured from the wafer W, the gate Since no charges are accumulated in the electrodes, it is possible to prevent the gate oxide film from being deteriorated or destroyed, and since energetic particles are not irradiated to the electronic device, the occurrence of crystal defects in the CCD sensor 200 can be prevented. Furthermore, since an unexpected chemical reaction caused by plasma does not occur, the generation of impurities can be prevented, thereby preventing the chamber 38 and the chamber 50 from being contaminated.

  Furthermore, according to the substrate processing method of the present embodiment, the wafer W is subjected to the dry cleaning process and the upper layer of the insulating film 261 is removed, so that the change in physical properties of the surface of the wafer W can be suppressed. Therefore, it is possible to reliably prevent a decrease in wiring reliability in the CCD sensor 200 manufactured from the wafer W.

  Therefore, according to the substrate processing method of the present embodiment, the removal amount of the insulating film can be accurately controlled without damaging the electronic device. Thereby, the insulating film can be thinned.

As described above, the substrate processing method according to the present embodiment is not limited to the one applied when the planarizing film for forming the color filter of the CCD sensor or the protective film for the color filter is formed to a desired thickness. In other electronic devices, the present invention can also be applied to the case where the thickness of the insulating film made of SiO ₂ is accurately formed to a desired thickness. For example, the substrate processing method can be applied to thinning an insulating film or an interlayer insulating film formed immediately above the wafer W.

  Further, as described above, the substrate processing method according to the present embodiment is not limited to the one used for manufacturing the CCD sensor, but other electronic devices, for example, at least an optically transparent insulating surface. It may be used for manufacturing a thin film device for a CCD having the above thin film.

  Furthermore, the CCD sensor is not limited to the above-described CCD sensor 200, and may have other configurations. For example, the CCD sensor 200 may include a light transmissive electrode made of an amorphous thin film formed by a CVD method instead of the silicon nitride film 252.

  The present invention is not limited to the above-described embodiment. For example, the present invention may be a method for manufacturing an electronic device including the above-described substrate processing method, a method for manufacturing a solid-state imaging device, or a method for manufacturing a thin film device for CCD. Good.

  FIG. 8 is a plan view showing a schematic configuration of a first modification of the substrate processing apparatus to which the substrate processing method according to the present embodiment is applied. In FIG. 8, the same components as those in the substrate processing apparatus 10 of FIG. 1 are denoted by the same reference numerals, and the description thereof is omitted.

  In FIG. 8, a substrate processing apparatus 137 includes a hexagonal transfer unit 138 in plan view, four process units 139 to 142 arranged radially around the transfer unit 138, a loader unit 13, a transfer unit 138, and Two load / lock units 143 and 144 that are arranged between the loader unit 13 and connect the transfer unit 138 and the loader unit 13 are provided.

  The transfer unit 138 and the process units 139 to 142 are maintained at a vacuum in the internal pressure, and the transfer unit 138 and the process units 139 to 142 are connected to each other via vacuum gate valves 145 to 148, respectively.

  In the substrate processing apparatus 137, the internal pressure of the loader unit 13 is maintained at atmospheric pressure, while the internal pressure of the transfer unit 138 is maintained at vacuum. Therefore, each load / lock unit 143, 144 is provided with vacuum gate valves 149, 150 at the connection with the transfer unit 138, and with atmospheric door valves 151, 152 at the connection with the loader unit 13, respectively. It is configured as a vacuum preliminary transfer chamber that can adjust the internal pressure. Each of the load / lock units 143 and 144 has wafer mounting tables 153 and 154 for temporarily mounting the wafer W delivered between the loader unit 13 and the transfer unit 138.

  The transfer unit 138 includes a frog-leg type transfer arm 155 disposed inside the transfer unit 138. The transfer arm 155 includes the process units 139 to 142 and the load / lock units 143 and 144. The wafer W is transferred between them.

  Each process unit 139 to 142 has a mounting table 156 to 159 on which a wafer W to be processed is mounted. Here, the process unit 140 has the same configuration as the first process unit 25 in the substrate processing apparatus 10, the process unit 141 has the same configuration as the second process unit 34, and the process unit 142 has the third configuration. The process unit 36 has the same configuration. Therefore, the process unit 140 can perform RIE processing on the wafer W, the process unit 141 can perform COR processing on the wafer W, and the process unit 142 can perform PHT processing on the wafer W.

In the substrate processing apparatus 137, similarly to the substrate processing apparatus 10 described above, an insulating film 261 having a predetermined thickness made of SiO ₂ is formed in order to form the planarizing film 253 and the protective film 258 having a desired thickness. The wafer W (see FIG. 7A) is loaded into the process unit 141 and subjected to COR processing, and further loaded into the process unit 142 and subjected to PHT processing, whereby the substrate processing according to the above-described embodiment is performed. Execute the method.

  The operation of each component in the substrate processing apparatus 137 is controlled by a system controller having the same configuration as the system controller in the substrate processing apparatus 10.

  FIG. 9 is a plan view showing a schematic configuration of a second modification of the substrate processing apparatus to which the substrate processing method according to the present embodiment is applied. In FIG. 9, the same components as those in the substrate processing apparatus 10 of FIG. 1 and the substrate processing apparatus 137 of FIG. 9 are denoted by the same reference numerals, and description thereof is omitted.

  In FIG. 9, the substrate processing apparatus 160 has two process units 161 and 162 added to the substrate processing apparatus 137 of FIG. 8, and correspondingly, the shape of the transfer unit 163 is also the transfer in the substrate processing apparatus 137. Different from the shape of the unit 138. The two added process units 161 and 162 are connected to the transfer unit 163 via vacuum gate valves 164 and 165, respectively, and have wafer W mounting tables 166 and 167, respectively.

  The transfer unit 163 includes a transfer arm unit 168 including two SCARA arm type transfer arms. The transfer arm unit 168 moves along a guide rail 169 disposed in the transfer unit 163, and moves the wafer W between the process units 139 to 142, 161, 162 and the load / lock units 143, 144. Transport.

In the substrate processing apparatus 160, similarly to the substrate processing apparatus 137, the wafer W on which the insulating film 261 having a predetermined thickness made of SiO ₂ is formed in order to form the planarizing film 253 and the protective film 258 having a desired thickness. (See FIG. 7A) is carried into the process unit 141 and subjected to COR processing, and further carried into the process unit 142 and subjected to PHT treatment, whereby the substrate processing method according to the present embodiment described above is performed. Execute.

  The operation of each component in the substrate processing apparatus 160 is also controlled by a system controller having the same configuration as the system controller in the substrate processing apparatus 10.

  In addition to the so-called semiconductor devices, the above-described electronic devices include non-volatile or large-capacity capacitors having a thin film made of a material having an insulating metal oxide such as a ferroelectric or a high dielectric, particularly a perovskite crystal structure. Also includes a memory element. Examples of the substance having a perovskite crystal structure include lead zirconate titanate (PZT), barium strontium titanate (PST), and niobium strontium bismuth tantalate (SBT).

  Another object of the present invention is to supply a storage medium storing software program codes for realizing the functions of the above-described embodiment to the EC 89 and store the computer (or CPU, MPU, etc.) of the EC 89 in the storage medium. It is also achieved by reading and executing the programmed program code.

  In this case, the program code itself read from the storage medium realizes the functions of the above-described embodiment, and the program code and the storage medium storing the program code constitute the present invention. .

  Examples of the storage medium for supplying the program code include a floppy (registered trademark) disk, a hard disk, a magneto-optical disk, a CD-ROM, a CD-R, a CD-RW, a DVD-ROM, a DVD-RAM, and a DVD. An optical disc such as RW or DVD + RW, a magnetic tape, a nonvolatile memory card, a ROM, or the like can be used. The program code may be downloaded via a network.

  Further, by executing the program code read by the computer, not only the functions of the present embodiment are realized, but also an OS (operating system) running on the computer based on the instruction of the program code, etc. Includes a case where part or all of the actual processing is performed and the above-described functions of the present embodiment are realized by the processing.

 Further, after the program code read from the storage medium is written in a memory provided in a function expansion board inserted into the computer or a function expansion unit connected to the computer, the expanded function is based on the instruction of the program code. This includes a case where the CPU or the like provided on the expansion board or the expansion unit performs part or all of the actual processing and the above-described functions of the present embodiment are realized by the processing.

  The form of the program code may be in the form of object code, program code executed by an interpreter, script data supplied to the OS, and the like.

1 is a plan view showing a schematic configuration of a substrate processing apparatus to which a substrate processing method according to an embodiment of the present invention is applied. 2 is a cross-sectional view of a second process unit in FIG. 1, FIG. 2A is a cross-sectional view taken along line II-II in FIG. 1, and FIG. 2B is an enlarged view of portion A in FIG. FIG. It is a perspective view which shows schematic structure of the 2nd process ship in FIG. It is a figure which shows schematic structure of the dry air supply system for unit drive of the 2nd load lock unit in FIG. It is a figure which shows schematic structure of the system controller in the substrate processing apparatus of FIG. FIG. 6A is a diagram showing a schematic configuration of a CCD sensor to which the substrate processing method according to the present embodiment is applied, and FIG. 6A is a diagram for explaining elements on the wafer W in the CCD sensor. B) is a partial sectional view of the CCD sensor. It is process drawing which shows the processing method of the board | substrate concerning this Embodiment. It is a top view which shows schematic structure of the 1st modification of the substrate processing apparatus with which the substrate processing method which concerns on this Embodiment is applied. It is a top view which shows schematic structure of the 2nd modification of the substrate processing apparatus with which the substrate processing method which concerns on this Embodiment is applied.

Explanation of symbols

W wafer 10, 137, 160 substrate processing apparatus 11 first process ship 12 second process ship 13 loader unit 17 first IMS
18 Second IMS
25 First process unit 34 Second process unit 36 Third process unit 37 Second transfer arm 38, 50, 70 Chamber 39 ESC
40 Shower head 41 TMP
42, 69 APC valve 45 First buffer chamber 46 Second buffer chamber 47, 48 Gas vent 49 Second load lock chamber 51 Stage heater 57 Ammonia gas supply pipe 58 Hydrogen fluoride gas supply pipe 59, 66, 72 Pressure gauge 61 Second process unit exhaust system
65, 71 Nitrogen gas supply pipe 67 Third process unit exhaust system 73 Second load / lock unit exhaust system 74 Atmospheric communication pipe 89 EC
90, 91, 92 MC
93 switching hub 95 GHOST network 97, 98, 99 I / O module 100 I / O unit 138, 163 transfer unit 139, 140, 141, 142, 161, 162 process unit 170 LAN
171 PC
200 CCD sensor 200
210 Photoelectric conversion element 220 Vertical transfer electrode part 221 Transfer electrode 222 Interlayer insulating film 223 Light-shielding curtain 251 Insulating film 253 Flattening film 254 Color filter 258 Protective film 261 Insulating film 262 Product layer

Claims (17)

A method of manufacturing a solid-state imaging device,
An insulating film exposure step of exposing the insulating film provided on the substrate of the solid-state imaging device to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure;
An insulating film heating step of heating the insulating film exposed to the mixed gas atmosphere to a predetermined temperature.   2. The method of manufacturing a solid-state imaging device according to claim 1, wherein the insulating film exposing step performs a plasmaless etching process on the substrate.   3. The method of manufacturing a solid-state imaging device according to claim 1, wherein the insulating film exposing step performs a dry cleaning process on the substrate.   Determination of a product generation condition for measuring the shape of the insulating film and determining at least one of a volume flow rate ratio of the hydrogen fluoride to the ammonia in the mixed gas and the predetermined pressure according to the measured shape The method according to claim 1, further comprising a step. The volume flow ratio of the hydrogen fluoride to the ammonia in the mixed gas is 1 to 1/2, and the predetermined pressure is 6.7 × 10 ^{−2 to} 4.0 Pa. The manufacturing method of the solid-state image sensor of any one of thru | or 4.   The method for manufacturing a solid-state imaging device according to claim 1, wherein the predetermined temperature is 80 to 200 ° C. 6. A method of manufacturing a solid-state imaging device,
A film thickness determining step for determining a desired film thickness of an insulating film included in the substrate of the solid-state imaging device;
A pre-process shape measuring step for measuring the shape of the insulating film;
A processing condition determining step of comparing the measured shape with the determined film thickness to determine a first processing condition and a second processing condition;
An insulating film exposure step of exposing the insulating film to an atmosphere of a mixed gas containing ammonia and hydrogen fluoride under a predetermined pressure based on the first processing condition;
And a step of heating the insulating film exposed to the mixed gas atmosphere to a predetermined temperature based on the second processing condition. A post-processing shape measuring step for measuring the shape of the insulating film after the insulating film heating step;
A processing condition changing step of changing the first processing condition and the second processing condition by comparing the shape measured in the post-processing shape measurement step with the determined film thickness; The method for manufacturing a solid-state imaging device according to claim 7.   The first processing condition is at least one of a volume flow ratio of the hydrogen fluoride to the ammonia in the mixed gas and the predetermined pressure, and the second processing condition is the predetermined temperature. The method for producing a solid-state imaging device according to claim 7 or 8, A plurality of photoelectric conversion elements provided in a matrix on a substrate, an insulating film formed on the substrate provided with the plurality of photoelectric conversion elements, and a switching element formed adjacent to the photoelectric conversion elements And a signal charge transfer electrode composed of a wiring, an interlayer insulating film formed on the signal charge transfer electrode, and a light shielding film made of a metal film formed on the signal charge transfer electrode via the interlayer insulating film A method of manufacturing a solid-state imaging device comprising:
A metal film forming step of forming the metal film to form the light shielding film;
A resist patterning step of forming a resist of a predetermined pattern for forming the light-shielding film on the deposited metal film;
A patterning step of patterning the interlayer insulating film by dry etching to form the light-shielding film and the hole, respectively, to the vicinity immediately above the metal film and the photoelectric conversion element using the resist;
A resist removing step for removing the resist;
A silicon nitride film forming step of forming a silicon nitride film in a recess defined by the light shielding film and the hole;
Applying a transparent insulating material having a refractive index lower than that of the silicon nitride film to form a first insulating layer and flattening the first insulating layer to form a flattening film; and
A color filter forming step of forming a color filter on the planarizing film;
A protective film forming step of forming a second insulating layer on the color filter and forming a protective film by thinning the second insulating layer;
Insulating film exposure in which the planarizing film forming step and the protective film forming step expose the first insulating layer and the second insulating layer to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure. And a step of heating an insulating film that heats the first insulating layer and the second insulating layer exposed to the mixed gas atmosphere to a predetermined temperature, respectively. Method. A light receiving portion forming step for forming a plurality of light receiving portions on the substrate for generating signal charges in response to light received; an insulating film forming step for forming an insulating film on the substrate on which the light receiving portion is formed; A signal charge transfer part forming step for forming a signal charge transfer part for transferring the signal charge obtained in the light receiving part; a light shielding film forming step for forming a conductive light shielding film on the signal charge transfer part; and the insulating film A light-transmitting electrode forming step of forming a light-transmitting electrode made of an amorphous silicon thin film directly on the light-shielding film and by CVD on the plurality of light-receiving portions. And
The insulating film forming step includes applying an insulating material on the substrate on which the light-receiving portion is formed to form the insulating film; and applying the applied insulating material with ammonia under a predetermined pressure. A solid-state imaging comprising: an insulating film exposure step for exposing to an atmosphere of a mixed gas containing hydrogen fluoride; and an insulating material heating step for heating the insulating material exposed to the mixed gas atmosphere to a predetermined temperature. Device manufacturing method. A method of manufacturing a thin film device for a CCD comprising a plurality of chips having the same shape pattern formed on a substrate and an insulating thin film that is optically transparent at least on the surface,
A film forming step of forming an insulating film to form the thin film;
Exposing the insulating film to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure; and
A film heating step of heating the insulating film exposed to the mixed gas atmosphere to a predetermined temperature;
A film inspection step for inspecting a predetermined condition for the heated insulating film at a predetermined inspection location in each of the plurality of chips;
A transporting step of transporting the thin film device to move to the next step when the insulating film satisfies the predetermined condition at the inspection location in each chip in the film inspection step. A method for manufacturing a thin film device. A program for causing a computer to execute a substrate processing method,
An insulating film exposure module that exposes the insulating film of the substrate to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure;
An insulating film heating module for heating an insulating film exposed to the mixed gas atmosphere to a predetermined temperature. A program for causing a computer to execute a method for manufacturing a solid-state imaging device,
A film thickness determination module that determines a desired film thickness of an insulating film included in the substrate of the solid-state imaging device;
A pre-process shape measurement module for measuring the shape of the insulating film;
A processing condition determination module that compares the measured shape with the determined film thickness to determine a first processing condition and a second processing condition;
An insulating film exposure module that exposes the insulating film to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure based on the first processing condition;
An insulating film heating module for heating an insulating film exposed to the mixed gas atmosphere to a predetermined temperature based on the second processing condition. A plurality of photoelectric conversion elements provided in a matrix on a substrate, an insulating film formed on the substrate provided with the plurality of photoelectric conversion elements, and a switching element formed adjacent to the photoelectric conversion elements And a signal charge transfer electrode composed of a wiring, an interlayer insulating film formed on the signal charge transfer electrode, and a light shielding film made of a metal film formed on the signal charge transfer electrode via the interlayer insulating film A program for causing a computer to execute a method for manufacturing a solid-state imaging device comprising:
A metal film forming module for forming the metal film to form the light shielding film;
A resist patterning module for forming a resist of a predetermined pattern for forming the light-shielding film on the deposited metal film;
A patterning module that forms the light shielding film and the hole by patterning the interlayer insulating film by dry etching up to the top of the metal film and the photoelectric conversion element using the resist, and
A resist removal module for removing the resist;
A silicon nitride film forming module for forming a silicon nitride film in a recess defined by the light shielding film and the hole;
Applying a transparent insulating material having a lower refractive index than the silicon nitride film to form a first insulating layer and flattening the first insulating layer to form a flattening film;
A color filter forming module for forming a color filter on the planarizing film;
A protective film forming module that forms a second insulating layer on the color filter and forms a protective film by thinning the second insulating layer;
Insulating film exposure in which the planarizing film forming module and the protective film forming module expose the first insulating layer and the second insulating layer to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure. A program comprising: a module; and an insulating film heating module that heats the first insulating layer and the second insulating layer exposed to the mixed gas atmosphere to a predetermined temperature. A light receiving part forming module for forming a plurality of light receiving parts on the substrate for generating a signal charge in response to received light; an insulating film forming module for forming an insulating film on the substrate on which the light receiving part is formed; A signal charge transfer part forming module for forming a signal charge transfer part for transferring a signal charge obtained in the light receiving part; a light shielding film forming module for forming a conductive light shielding film on the signal charge transfer part; and the insulating film A solid-state imaging device manufacturing method comprising: a light-transmitting electrode forming module that forms a light-transmitting electrode made of an amorphous silicon-based thin film on the plurality of light-receiving portions and directly on the light-shielding film through a CVD method via a computer A program to be executed,
The insulating film forming module includes: an insulating material application module that applies an insulating material on a substrate on which the light receiving unit is formed to form the insulating film; and the applied insulating material with ammonia under a predetermined pressure. A program comprising: an insulating film exposure module for exposing to an atmosphere of a mixed gas containing hydrogen fluoride; and an insulating material heating module for heating the insulating material exposed to the mixed gas atmosphere to a predetermined temperature. A program for causing a computer to execute a method of manufacturing a thin film device for a CCD comprising a plurality of chips having the same shape pattern formed on a substrate and an insulating thin film that is optically transparent at least on the surface,
A film forming module for forming an insulating film to form the thin film;
A film exposure module for exposing the insulating film to a mixed gas atmosphere containing ammonia and hydrogen fluoride under a predetermined pressure;
A film heating module for heating the insulating film exposed to the mixed gas atmosphere to a predetermined temperature;
A film inspection module for inspecting a predetermined condition for the heated insulating film at a predetermined inspection location in each of the plurality of chips;
The film inspection module includes a transfer module that transfers the thin film device to the next step when the insulating film satisfies the predetermined condition at the inspection location in each chip. Program.