TW522464B - Method of fabricating semiconductor device and wafer treatment apparatus employed thereof as well as semiconductor device - Google Patents

Abstract

This invention provides: a method of fabricating semiconductor device with high selectivity; a wafer treatment apparatus employed in such fabrication method; as well as semiconductor device fabricated by the method. In the wafer treatment apparatus, a hydrofluoric acid gas supply pipe (5) and an evacuation pipe (4) are connected to a chamber (1) storing a wafer (2) for performing prescribed treatment. A control part (11) is provided for controlling supply of hydrofluoric acid gas. The control part (11) sets a time for supplying the hydrofluoric acid gas into the chamber (1) to be longer than a time up to starting of etching of a reaction product and shorter than a time up to starting etching the gate insulator film.

Description

522464 A7 ----------- B7___ V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a method for manufacturing a semiconductor device, a wafer processing device used in the method, and a gate electrode The cleaning method after the electrode formation is related to a semiconductor device manufacturing method with high etching selectivity; the cleaning method after the electrode formation is free, a wafer processing device used for the manufacturing method or the cleaning method; and A semiconductor device obtained by the manufacturing method. [Conventional Technology] In a semiconductor device, in particular, a transistor used in a logic circuit or a system LSI is required to have high performance. To meet this requirement, the gate insulating film thickness in the transistor is set to 3 nm or less. In recent years, a thinner gate insulating film with a thickness smaller than 2 nm has been developed. In terms of etching the gate electrode of the transistor, the conductive layer that actually forms the gate electrode is etched in accordance with the conditions of high selectivity to the insulator, and the thin gate insulator is prevented from being etched. In the rest of the time when the gate electrode is formed, the reaction product 'produced at the time of touching' will be attached to the surface of the side wall of the gate electrode or the printed circuit board of the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economics and Economics. The surface of the masking material to be cased. Observation with an SEM (electron microscope) 'This reaction product is in conformal form-such as attached to the surface. To ensure the reliability of the semiconductor device, it is necessary to remove the reaction products attached to the surface of the gate electrode. In order to remove such reaction products, a wet cleaning method using a chemical solution has conventionally been used. Hereinafter, a method for manufacturing a semiconductor device including the wet cleaning will be described. Insulation of paper edge film 1

312940A 522464 A7 V. Description of the invention (2) Membrane. A multi-film as a closed electrode is formed on the insulating substrate. A predetermined process is performed on this dream crystal film to form a masking material. This masking material is used as a mask. For example & quasi-experiment, polycrystalline stone is used in a plasma of a mixed gas containing C12 and 〇2 or a mixed gas containing HBr, cl2 and 02. The film is subjected to an engraving process to thereby pattern the interelectrode. During patterning, reaction products adhere to the surface of the side wall portion of the interelectrode electrode or the surface of the mask material. After the closed electrode is formed, it is washed with moisture to remove the reaction products attached to the gate electrode. In particular, a mixed gas containing CU and 〇2 or a mixed gas containing HBr, cl2, and 〇2 force is electrically mass-applied, and the reaction product is SiOxCly or SiOxBry. It is generally known, and its main component is For silicon oxide. In this manner, the semiconductor substrate is immersed in a cleaning solution such as dilute hydrofluoric acid or hydrogen peroxide ammonia (NΗ40Η + Η22 + 2 + Η2 ··· APM) to remove the reaction product. Thereby, reaction products can be removed. In addition, after the reaction product is removed, in order to electrically connect the wiring and the gate electrode by tungsten buried in the contact hole, the masking material remaining on the gate electrode must be removed. This masking material is a silicon oxide film such as a TEOS oxide film. Therefore, the mask formed by the silicon oxide film can be removed by, for example, dilute hydrofluoric acid '. As a result, the silicon oxide film as a mask will be removed to form a gate electrode. [Problems to be Solved by the Invention] However, the conventional method for manufacturing a semiconductor device has the following problems. As mentioned above, when forming the gate electrode, the paper size attached to the side wall of the gate electrode is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm). Please read the four items on the back, and then complete this note. Page order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs

312940A 522464 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention The reaction products on the surface are mainly composed of silicon oxide films such as SiOxciy4 SloxBry. On the other hand, the gate insulation film is It is formed by silicon oxide obtained by oxidizing a silicon substrate. Therefore, when the reaction product is removed by a cleaning solution such as dilute acid (DHF) or hydrogen peroxide ammonia water (αρμ), it will also be at the gate electrode. The insulating film is etched. Therefore, as indicated by the marked portion 105 in FIG. 27, the portion of the gate insulation 臈 102 between the silicon substrate 10 and the gate electrode 103 is etched. A situation in which a notch portion of the gate electrode 103 is exposed. Therefore, a current leakage occurs from the exposed notch portion of the gate electrode 103, and the electrical characteristics of the transistor deteriorate, which reduces the reliability of the semiconductor device. In addition, As shown in FIG. 28, when the gate electrode is a gate electrode 103 made of a polysilicon (Polycide) structure formed by a polycrystalline silicon film 103a and a tungsten silicide film 103b, it is intended to use hydrogen peroxide. Ammonia (ApM) will react When the product is removed, in addition to the gate insulating film 102 (part 105 of the marked area), the sidewall portion of the tungsten silicide film 103b is also subjected to an etching treatment (the side is left etched). In this case Next, when the gate electrode is covered with an interlayer insulating film, a problem that a void is formed without being etched is extremely likely to occur, which is one of the main reasons for reducing the reliability of a semiconductor device. In addition, as described above, by dilute hydrofluoric acid The silicon oxide film used as a mask will be removed. However, because the gate insulating film is also formed of a silicon oxide film, the masking material will be removed and the etching will be performed on the gate insulating film. This paper is suitable for China National Standard (CNS) A4 Specification (210 X 297 Meals

312940A --------- Aw -------- Order --------- line (Please read the precautions on the back before filling this page) 522464

Fifth, the description of the invention (4). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, as shown in Figure 29, a part of the gate insulation _ 102 between the Xiao gate electrodes 103 on the Shixi substrate 1G1 is exposed, and the gate electrode 103 is exposed. The lower corner is 105. The result is the same as that in the case of removing the reaction product, and a problem arises in that a current leaks from the corner portion 105 below the exposed electrode and leaks I to reduce the electrical characteristics of the transistor. One of the objects of the present invention is to provide a method for manufacturing a semiconductor device capable of obtaining high selectivity in etching. Another object is to provide a method for manufacturing such a semiconductor device = a wafer processing device. Yet another object is to provide a semiconductor device obtainable by such a semiconductor device manufacturing method. [Means for Solving the Problem] A method for manufacturing a semiconductor device according to one aspect of the present invention is a method for manufacturing a two-device device. The method includes using a second part formed on a semiconductor substrate and having predetermined etching characteristics. _The first minute of the characteristic is performed ::: aerobic: pre :: == pre-processed wafer processing. At this wafer ::::: The gas is introduced into the container, and the time from when the gas is supplied to the container by the gas supply process 2_ is used as the first start time. The time until the second part of the start of the second part is used as the second device, which is shorter than the start time of the second. It will be longer than the first one. This paper size applies the Chinese national standard (CN & A4 specification⑵0 X 297). Please ‘read the notes on the back ^ first and then fill out this page. 订 Thread 312940Α 522464

V. Description of the invention (5) The door of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the door 'according to this manufacturing method', because the etching gas supply project will be implemented, it will be longer than the first start time 'and shorter than the second start time, Therefore, before the start of the second part, the first part is etched to the right. As a result, it is possible to selectively perform the first division without actually etching the first row. Specifically, the time difference between the first start time and the second start time should ideally be set to 5 seconds or less. In this case, as will be described later, for example, it is possible to selectively remove only the reactive product without the need for a surname insulation film. Ideally, it is preferable to have: a step of forming an insulating film on the semiconductor substrate; and a step of forming a conductive region on the insulating pad, and the step of forming the insulating film includes a step of forming a gate insulating pad; and a step of forming a conductive region It includes a step of forming a gate electrode portion on the gate insulating film. The first part is generated when the gate electrode portion is formed, and includes a reaction product covering the surface of the gate insulating film and the surface of the gate electrode portion. The second part includes The gate insulating film, and the gas used for etching includes a hydrofluoric acid gas. At this time, when the reaction product attached when the gate electrode portion is formed is removed, the reaction product can be selectively etched without selectively removing the gate insulation film, and the reaction product can be selectively removed. Thing. In addition, the "ideally" wafer processing step preferably includes an additional gas supply step for introducing a reaction-promoting gas to shorten the first start time before the etching gas supply step. At this time, the first start time can be shortened by the reaction-promoting gas. Read the notes on the back ^ and fill in this page.) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2〗 0 X 297 mm) 5

312940A 522464 members The result ’will shorten the crystal A7 V. Description of the invention (6) Longer etching time for the first part Round processing time for the round processing step. = 外 'Ideally, a gas supply step and an etching gas supply step can be performed in the hafnium processing step.仃 Add In this way, by performing the Add # supply step interactively, the second part a body supply step and the last name gas can be removed.卩 ... select the first part. Ideally, the additional gas supply step in the wafer processing process continues after the start of the gas supply step. At this time, the etching speed in the etching gas supply step can be increased to reduce the processing time of the wafer processing step. In addition, ideally, the wafer processing step is preferably provided with a capacity number = :::: exhaust step 'at least in the-gas supply efficiency ㈣ processing = to the * part of the ~ ~ ㈤ good equipped with. In the semiconductor A step of forming a conductive layer through a gate insulating film on the substrate; a step of forming a masking layer on the conductive layer ^, using the material layer as a material and forming the conductive layer by performing a engraving process on the conductive layer The step of the gate electrode '· the step of removing the mask layer remaining on the closed electrode after the formation of the inter-electrode, and the wafer processing engineering step includes the step of removing the mask layer' and the section] includes The masking layer contains the aforementioned gate insulation 臈 'and is in Zhaozhaotian. This paper standard is applicable to Zhongguanjia Standard (CNS) A4 specifications (publication)-,,, and steps

6 312940A — -------- ^ --------- (Please read the note at the back? Matters before filling out this page) 522464 A7

5. Description of the invention (7) refers to the supply of hydrofluoric acid gas as an off-gas. At this time, when the gate electrode patterned masking layer is removed, there is no need to actually etch the gate insulating film, but the masking layer can be selectively etched and the masking layer can be selectively removed. In addition, it is desirable that the etching gas supply step is performed repeatedly in the wafer processing step. Thereby, even when the mask layer cannot be removed by one etching, the etching gas supply step can be repeatedly performed without actually etching the gate insulating film, and the layer that becomes the mask can be reliably removed. In addition, it is more desirable that the wafer processing step be provided with an exhaust step capable of exhausting the inside of the container, and can be used for a general gas supply step and an exhaust step. Thereby, in the gas supply step for etching, the pressure in the container is increased, and the layer to be a mask can be effectively etched. The semiconductor device according to another aspect of the present invention is a semiconductor device manufactured by the semiconductor device manufacturing method of item i in item 1 to item 10 of the patent application scope. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. According to the semiconductor device, the second part can be selectively etched. The reaction product attached when the gate electrode is formed will not etch the actual gate insulating film. To remove it. In addition, the mask layer when the gate electrode is formed can be removed without leaving a substantial interlayer insulating film. As a result, electrical deterioration of the semiconductor device can be prevented.

V. Description of the invention (8) part and the second part of the 4th characteristic Japanese yen processing device which performs a predetermined process with a characteristic different from the predetermined etching characteristic, and has a gas supply unit for etching and a sintering machine There is a container gas for Qiu H, and this state is used to contain wafers. Etching milk supply ... P is used to supply etching gas. It is used to control the supply of etching gas to the 7 ° control unit, which controls the supply of etching gas to Gu Pi. / The diameter control section is equipped with the following functions. After the start of the i part, the second and second parts will be: the gas for the engraving is introduced into the chamber, and the gas for the etching is introduced. When the first and second start time is taken as the second start time, the second start time is longer than the first time, the start time of Father 1 is longer, and the time is shorter than the second start time. In the wafer processing supply unit, the etching gas is supplied to the container. According to this wafer processing apparatus, only the first portion is etched in the first month of the second month, so there is no need to actually etch the first portion. Part 2, ^ optionally left part 1 Thereby, for example, when the reaction product attached when the gate electrode of the semiconductor device is formed is removed in the remaining time, 'there is no need for an actual insulation insulator, and only the reaction product can be selectively removed, and Prevents deterioration of electrical characteristics of semiconductor devices. In particular, in this wafer processing apparatus, when the time difference between the j-th start time and the second start time is 5 seconds or less, the first portion can be selectively and reliably etched. Ideally, it is desirable to include an additive gas supply unit for supplying a reaction promoting gas for shortening the first initiation time to the container, and the control unit includes: before supplying the etching gas, the reaction promoting gas can be added by The function of supplying air to the container. 8 paper rule Chinese National Standard (CNS) A4 size ⑵0 x 297 meals

312940A 522464 A7 V. Description of the invention (9) At this time, the first starting time is shortened by Laoshan c by the reaction-promoting gas, so it will make the remaining part of the first part of the processing 丨 iron buried time longer. As a result, the processing time can be shortened, and the throughput of the wafer processing facility can be improved. In addition, ideally, the control of the county P should include functions that can alternately supply the etching gas supply and the reaction promotion gas supply. At this time, by using the gas supply for narration and: The gas supply should be promoted alternately. The first part can be repeatedly touched and the second part can be left to selectively and surely remove the first part. More preferably, the control section is the most crowded, and it includes the following: during the supply of etching gas, the function of supplying the reaction promoting gas is also implemented. In this case, by supplying the reaction-promoting gas during the supply of the gas for the money engraving, it is possible to increase the speed of engraving when the first part is engraved. Thereby, the processing time will be shortened 'and the production capacity of the wafer processing apparatus can be improved. Ideally, it is preferable to include an exhaust section for exhausting the inside of the container; the control section includes at least a function of stopping the exhaust section when the etching gas is supplied. At this time, as compared with the case where the usual exhaust is performed, the pressure in the container will be increased when the last-name gas is supplied, and the ^ portion can be effectively performed for # moments. The gate electrode cleaning method in another form of the present invention has the following characteristics: after interposing an interlayer insulating film on a semiconductor substrate and using a mask to perform a remainder to form a patterned gate electrode ， The reaction products produced by # 刻 are removed by the hydrogen acid gas. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 male ®)

312940A — # 4 (Please read the note and pay attention to this item before filling out this page) Order --------- Multiple Printing of Clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 9 522464 A7

5. Description of the invention (10) According to the cleaning method after the gate electrode is formed, the gate insulation film does not need to be removed, and the reaction product can be removed. Ideally, the 'gate electrode is composed of at least a film containing silicon. At this time, the main component of the reaction product generated when the gate electrode formed by the silicon-containing film is formed, and the cut oxide can be removed by the hydrogen acid gas without removing the interlayer insulating film. It can remove reaction products. In addition, it is characterized in that, ideally, the time for removing the reaction product by the hydrofluoric acid gas is 'preferably at the time of the cutting of the reaction product III with the hydrofluoric acid gas' and the gate insulating film Within the response time difference at the moment of cutting. At this time, 'the gate insulation film does not need to be cut, and only the reaction product can be removed. In addition, it is characterized in that the reaction product is desirably removed by using a hydrofluoric acid gas by repeatedly setting the reaction time difference. Printed by the staff cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at this time 'really only the reaction product can be removed, specifically, the semiconductor substrate after the formation of the interelectrode is placed in a container, and the repeated setting of the reaction time difference is borrowed It is performed by repeatedly performing the container vacuumization step and the hydrofluoric acid gas filling step. 6 It is characterized in that it is desirable to set the set temperature when removing the reaction product by the hydrofluoric acid gas to a temperature lower than 4 (TC lower Temperature. In this case, the shortening of the reaction time difference will be controlled, so that the reaction products can be more easily removed. The lower limit of the set temperature is better at room temperature. This paper size applies the Chinese national standard (CNS ) A4 size (210 x 297 mm) 10

312940A 522464

312940A A7 V. Description of the invention (11) [Implementation mode of the invention] Chapter 1 Implementation mode: The method for manufacturing a semiconductor wafer processing method according to Embodiment 1 of the present invention will be described. Contain the Japanese Yen, not the βθ circle, and shovel the Japanese Yen 2 and container the wafer. This container contains two branches and three processes to hold the wafer 2: The outer burial volume ... 'is connected to the gas acid gas supply pipe 5 and true heart. Hydrofluoric acid gas can be supplied into the container by the fluoric acid supply pipe 5 The vacuum exhaust pipe 4 can make the room cry! Push in ... Make theft. And Gu Ang 1 is exhausted. The wafer virtual device includes a control unit U that controls the supply of hydrofluoric acid gas. Next, an example of a semiconductor device method using the wafer processing device will be described. First, as shown in FIG. 2, the method of method m is to form a silicide film 22 as a gate insulating film (up to 2 nm) by using, for example, a hot-oxygen clay plate. On the dream oxide film 22, a polycrystalline silicon film 23 serving as a gate electrode (up to 200 ⑽) is formed by, for example, a CVD method. The polycrystalline silicon film 23 2 is formed by, for example, a CVD method as a dream oxidation medium as a masking material (up to 50 ° F). Next, a silicon oxide film 24 is formed on the silicon oxide film 24 as shown in FIG. 3. A photoresist pattern 25 of a masking material is formed. Next, as shown in FIG. 4, the photoresist pattern 25 is used as a mask ', and an oxide film mask for patterning the gate electrode is formed on the dream oxide film 24 by a holmium process. Then, the photoresist pattern 25 is removed. Secondly, as shown in FIG. 5, the oxide film mask 24a is used as a mask, and a mixed gas containing Cl2 and 〇2, or a mixture containing HBr, Cl2, and 〇2, is used as the standard of the family ’s scale ( CNSM4_Special coffee, 7 meals) 11 ----------------- — Order ------- I (Please read the notes on the back and front before filling out this Page) Printed by the line & 522464 Employee Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs

312940A A7 V. Description of the invention (13) It is generally known that its main component is silicon oxide. When the reaction product 26 formed by the dream oxide reacts with hydrofluoric acid gas, water (H20) is generated. When the reaction continues and the amount of water generated exceeds a certain amount, the etching rate (cutting) will increase rapidly. In terms of the reaction product 26 and the silicon oxide film 22, the reaction rate of the reaction product% is faster than that of the silicon oxide film 22. Therefore, the time t1 when the amount of water produced by the reaction of the nitrogen acid gas and the reaction product 26 reaches a certain amount t1 is shorter than the time t2 when the amount of water produced by the reaction of the hydrofluoric acid gas and the silicon oxide film u reaches a certain amount. As a result, the reaction product 26 will be etched earlier than the silicon oxide film 22. Therefore, as shown in FIG. 7, the time t in the supply of hydrofluoric acid gas into the container is set to be longer than the etching start time of the reaction product 26, and is longer than that of silicon oxide 22, which is a gate insulating film. The etching start time is short, so that the silicon oxide film 22 does not need to be actually etched, and only the reaction product 26 can be selectively etched. … Thus, in practice, the reaction product 26 is only subjected to the time equivalent to the difference between time t and time u. By extending the time t to supply the nitrogen acid gas to time t2, The reaction product% is etched within the maximum time difference τ between time and time t2. At this time, since the diamond oxide film 22 is not subjected to the rhyme treatment, the stone evening substrate 21 is damaged. In addition, the time u and the time u are preferably obtained through experiments in advance. In addition, 'the reaction between the hydrofluoric acid gas and the reaction to generate tritium depends on the temperature setting', and I learned that the temperature in the container is set to _ ^^ (CNS) A4 secret coffee ~ 4 ° C or more- ---------------- Order --------- line (please read the precautions on the back before filling this page) A7 522464 、 Instruction of the invention (under 14 states) In this case, the time difference T becomes short, which is not practical. Therefore, it has been determined that it is better to set the temperature in the container to 4 (rc or lower) when etching the reaction product 26 of the silicon oxide film with sufficient selectivity. In addition, in the above-mentioned method of manufacturing a semiconductor device, a gate electrode formed of a polycrystalline silicon film has been exemplified as the gate electrode. Others, even a gate formed of a polycrystalline silicide formed of a polycrystalline silicon film and a metal silicide, etc. The electrode is used as the gate electrode. When the reaction products are removed, it is learned that the reaction between hydrofluoric acid gas and metal silicide rhenium hardly occurs, and the side surface of the interelectrode electrode is not etched. When the insulation film covers the gate electrode, there will be no voids. This improves the reliability of the semiconductor device. The second embodiment describes the method of manufacturing a semiconductor device according to the second embodiment. As described in the first embodiment, the reaction is performed only within a time corresponding to the time difference τ. When the product is etched, it may be difficult to completely remove the reaction product 26. In this case, as shown in FIG. 8, the reaction product 26 can be almost completely introduced and exhausted by hydrofluoric acid gas repeatedly. The method of etching is explained in detail below. In the step shown in FIG. 5 described in the first embodiment, first, as shown in FIG. 8, only the time before the etching of the reaction product 26 is started. It is longer than the time before the silicon oxide film 22 starts to be etched, and the hydrofluoric acid gas is introduced within the short time t. The hydrofluoric acid is introduced into the container 1 by the introduction of the hydrofluoric acid gas. The gas pressure will rise. No item in this paper applies the Zhongguanjia Standard (CNS) A4 specification (21G X 297 male f) ”(Please read the precautions on the back before filling this page) Order ----- ---- Wisdom of the Ministry of Economic Affairs Printed by the Consumers 'Cooperative of the Production Bureau 522464 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 _____ V. Description of the Invention (15) The silicon oxide film 22 is etched internationally, and only the reaction product 26 can be selectively etched. After that, the supply of hydrofluoric acid gas was stopped. Next, as shown in Fig. 8, the inside of the container! Was evacuated through the vacuum exhaust pipe to clean the inside of the container 1 and the surface of the wafer 2. It can reduce the pressure of hydrofluoric acid gas. In addition, the water produced by the reaction of hydrofluoric acid gas with the reaction product is also removed. Second, the hydrofluoric acid gas is introduced into the container j again only within the predetermined time t described above ( (2nd time) In this way, the remaining reaction product 26 can be selectively removed similarly to the etching performed by the first hydrofluoric acid gas. Hereinafter, by repeating this operation (step) for an appropriate number of times, the reaction product adhered to the gate electrode 23a can be almost completely removed without actually etching the silicon oxide film 22. In this embodiment, the upper limit of the time for introducing the hydrofluoric acid gas is set to a time t2 before the silicon oxide film 22 starts etching. However, "only in a state where the silicon oxide film is etched, the notch portion under the gate electrode is not exposed, and the leakage current can be reduced at the same time" or the side of the gate electrode is not etched In the following, the above time can be used as an upper limit, and a more effective reaction product 26 is etched.

The third embodiment is as described in the first embodiment. Generally, in the wafer processing apparatus, the time for supplying hydrofluoric acid is longer than the time before the reaction product 26 starts to etch, and the silicon oxide film 22 is etched. The time before was short. However, depending on the combination conditions of the reaction product and the gate insulating film, the time difference T (t2-11) may be lower than about 5 seconds. Therefore, the required paper size applies to the Chinese National Standard (CNS) A4 (21 × 297 mm)

312940A --------- 丨 ^^ -------- Order --------- line (Please read the precautions on the back before filling this page) 15 522464 A7 V. DESCRIPTION OF THE INVENTION (16) The switching operation of the introduction of the hydrofluoric acid gas and the switching operation of the exhaust gas must be performed at a relatively high speed. (Please read the precautions on the back before filling out this page.) In the third embodiment, when the reaction time difference τ is shorter than 5 seconds, the iterative operation of supplying and exhausting hydrofluoric acid gas can be performed more accurately. 'A wafer device which selectively and surely performs etching, and a semiconductor device manufacturing method using the device will be described in detail. As shown in Fig. 9, in this wafer device, the HF supply pipe 5 is provided with a pulse valve 6. The control unit i 丨 controls the switching of the pulse valve 6. The other components are the same as those of the wafer processing apparatus shown in FIG. 1 as described in the first embodiment, and therefore the same elements are designated by the same reference numerals and their descriptions are omitted. With the pulse valve 6 and the control unit u, the gadofluoric acid gas can be supplied to the container 1 in a very short time ranging from hundreds of microseconds to hundreds of milliseconds. Next, a method for manufacturing a semiconductor device using the wafer processing device will be described in detail. The steps up to Fig. 10 are the same as those shown in Figs. 2 to 5 described in the i-th embodiment. After that, Du Intellectual Property Department, Intellectual Property Bureau of the Ministry of Economic Affairs, cooperated with consumer printing and placed the wafer with the reaction product 26 on the wafer processing equipment. Next, 'the vacuum exhaust pipe 4 is opened, and the inside of the container j is evacuated to a predetermined vacuum state. After that, as shown in FIG. U, the time is only longer than the time before the reaction product 26 starts to be engraved, and the time is shorter than the time before the broken oxide 22 starts to etch. [Within, the pulse valve 6 is opened and the container is opened. Hydrofluoric acid gas is supplied in i (the second owe). The pressure of the hydrofluoric acid gas in the container 1 by the supply of hydrogen tritium gas will rise. This paper size applies to China National Standard (CNS) A4 specification (210 x 297 public meals ^ --------

16 312940A Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 17 522464 A7 _____B7____ V. Description of the Invention (Π) With the supply of hydrofluoric acid gas for a certain period of time, there is no need to actually etch the silicon oxide film 22, and it is possible to selectively etch only the reaction物 物 26。 26 products. The water generated after the hydrofluoric acid gas and the reaction product react with each other is discharged to the outside of the container 1 through the vacuum exhaust pipe 4. Then, the pulse valve 6 is opened at a predetermined time t to supply the hydrofluoric acid gas into the container 1 (second time). Thereby, the remaining reaction product 26 is selectively removed in the same manner as in the case of the first hydrofluoric acid etching. Afterwards, the control section 丨 丨 controls the switching of the pulse valve 6 and repeats this operation (step) only an appropriate number of times, whereby the reaction attached to the surface of the gate electrode 23a can be performed without actually etching the silicon oxide film 22 '. The product 26 is removed to a nearly complete degree. According to experiments, it is confirmed that the control unit 11 controls the opening and closing of the pulse valve 6 'to accurately supply the hydrofluoric acid gas into the container 1 even in a short period of time. For example, if a wafer processing apparatus without such pulse valve 6 is used, the time for supplying hydrofluoric acid gas is set to about 5 seconds, and the time for stopping the supply of hydrofluoric acid gas is set to about 60 seconds. As the gate insulation, the stone oxidized m 22 will be engraved to the inm㈣. In contrast, the wafer device will be used to supply the hydrofluoric acid gas at about 100 milliseconds, and the supply of hydrofluoride will be stopped. The time of the acid gas is set to about seconds, and the silicon oxide film 22 as the gate insulation is hardly touched during the processing. In this case, it is known that the materials used in the field are the reaction product and the insulating amine 1-soil, which is the gate insulation, and the stone oxidized film # T (t2-tl )in

312940A ϋ n ϋ n ϋ n ϋ n, f · ϋ ϋ n · ϋ n ϋ «ϋ 一 OJs an nnnnnn I n. (Please read the notes on the back before filling out this page) 5 Employees’ Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed ------- I. -__ Β7 ____ 5. Description of the Invention (18) A sample of about 1 second, but this wafer processing device can exert its effect more when the reaction time difference T is about 5 seconds or less ( Etch selectivity). Moreover, in this wafer device, although it has been described that the on / off of the supply of hydrofluoric acid gas can be controlled by the pulse valve 6, it is also possible to use a conductive material that can change the conductivity of the hydrofluoric acid gas supply pipe 5 at high speed. Flow regulator. At this time, the reaction product 26 can be selectively etched and removed by reducing the hydrofluoric acid gas flow flowing in a state where the flow rate regulator is closed to a level where the silicon oxide film is not etched. Chapter 4 Implementation Performance In the fourth embodiment below, a wafer processing apparatus having an additional gas supply pipe for supplying a gas for promoting a reaction between a hydrofluoric acid gas and a reaction product to a container, and using the same The semiconductor device manufacturing method of the device is explained in detail. As shown in Fig. 12, in the wafer processing apparatus, an additional gas supply pipe 7 is connected to the container 1, and the additional gas supply pipe 7t is further provided with a pulse valve 8. In addition to the pulse valve 6, the control unit 11 also controls the opening and closing of the pulse valve 8. In addition, the other components are the same as those of the wafer processing apparatus shown in FIG. 9 described in the third embodiment, and therefore the same elements are designated by the same reference numerals, and descriptions thereof are omitted. By opening and closing the pulse valve 8, the additional gas can be supplied to the container 1 in a very short time ranging from hundreds of microseconds to hundreds of milliseconds. Next, a method for manufacturing a semiconductor device using the wafer processing device will be described in detail. After the steps shown in FIG. 2 to FIG. 5 described in the first embodiment, the wafer to which the reaction product 26 is attached is placed on the wafer ϋ ai * iai nn ϋ ϋ ϋ I, I ϋ · ^ 1 nnnn ϋ n 口 π nn ϋ n 1 1— 1 · I 'I (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210x 297 mm) 18

312940A 522464 Printed by A7, a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and a Consumer Cooperative. V. Description of the invention (19 Round processing device support stand 3. This wafer processing device, before supplying hydrofluoric acid gas, first introduces additional gas such as water vapor into the container 1 First, the vacuum exhaust pipe 4 is opened, and the inside of the container 1 is evacuated to a predetermined vacuum state. Then, as shown in FIG. 13, the pulse valve 8 provided in the additive gas supply pipe 7 is opened, and The water vapor (H20) is supplied to the container 1 within a predetermined time. The water vapor supplied to the container 1 is attached to the surface of the reaction product 26 as shown in FIG. 14, and then, as shown in FIG. 13. The pulse valve 6 is opened for a time t longer than the time until the etching of the reaction product 26 is started, and shorter than the time before the etching of the silicon oxide film 22, and the hydrofluoric acid gas is supplied to the container ( 1st time. By the introduction of water vapor and the introduction of hydrofluoric acid gas, the pressure of the hydrofluoric acid gas in the container 1 will rise. As shown in FIG. Reaction of materials to produce SiF4 The reaction product 26 is selectively etched. As shown in FIG. 16, the generated siF4, H2O, and attached moisture are discharged to the outside of the container 1 through an exhaust pipe. Then, the pulse valve 8 is opened again, and water vapor is supplied (second time) to the container 1 to allow water vapor to adhere to the surface of the reaction product 26. Next, the pulse valve 6 is opened again to supply hydrofluoric acid gas ( (2nd time) to the inside of container i. With this, the remaining reaction product 26 can be selectively removed in the same manner as in the case of the first hydrofluoric acid etching. After that, it is controlled by the control unit Π The switching of the pulse valve 6 and § only repeats the operation (step) with a suitable number of people, thereby, without the substantial material of the silicon film 22 being left, it can be attached to the surface of the gate electrode 23a. Reaction

312940A ------ Order --------- line (please read the precautions on the back before filling this page) 522464 V. Description of the invention (2〇 ) The finished product 26 is almost completely removed. According to this wafer processing apparatus, 'by supplying water vapor before supplying hydrofluoric acid gas', moisture can be attached to the reaction product 26, and the reaction product 26 is performed by the ion of hydrofluoric acid (HF). The hydrofluoric acid gas' substantially supplied to the reaction product 26 can promote ionization by the moisture (h20) attached to the surface of the reaction product 26. As a result, the time ^ before the start of the reaction product 26 is shortened compared with the case where no moisture is adhered. On the other hand, since the wonderful oxide film 22 is almost covered by the reaction product% in a conformal manner (C0nf0rmal), moisture is hardly absorbed in the stone evening oxide film. Therefore, the time t2 until the time when the dream oxidation film performed by the hydrofluoric acid gas starts to be carved is hardly affected. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, in other words, as shown in FIG. 17, the time U until the reaction product begins to be engraved is shortened to become _, and the time before the start of the Shi Xi oxide film is etched. Time t2 has hardly changed. Thereby, even if the supply time of the secondary nitrogen acid gas is the same (for example, t2), the actual reaction time of the reaction product 26 can be extended from time τ to n, and the reaction can be selectively generated with a small number of repeated operations. Material is completely removed. In addition, although the description has been given of the case where on / off of the added gas supply is performed by the pulse 阙 8, if a conductive flow regulator capable of changing the hydrogen acid gas supply pipe 5 at high speed is used, water vapor can also be absorbed. Focusing on the reaction product, the above effects are obtained.簋 5 Embodiment In the fifth embodiment, the feature 55 丨 丨 B 1

20 312940A 522464 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

312940A A7 V. Description of the Invention (21) The wafer processing device using gas and the semiconductor device manufacturing method using the device will be explained in detail. As shown in FIG. 18, an exhaust pulse valve 9 is provided in the vacuum exhaust pipe 4 of the wafer processing apparatus. The control unit U controls the opening and closing of the pulse valve 9 for exhaust in addition to the pulse 阙 6. In other respects, since it is the same as the wafer device shown in FIG. 9 described in the third embodiment, the same elements are designated by the same symbols, and descriptions thereof are omitted. The control unit 11 controls the switching of the pulse valve 6 and the exhaust pulse valve 9 to alternately supply and discharge the hydrofluoric acid gas. In other words, as shown in Fig. M, the container is not vented during the supply of hydrofluoric acid gas, and the container is not vented during the supply of hydrofluoric acid gas. As described above ', since the venting is not performed when the hydrofluoric acid gas is supplied, the pressure in the container becomes higher when the gaseous acid gas is supplied than when the container is vented frequently. Thereby, the reaction product can be promoted and removed effectively. Next, a manufacturing method using the wafer processing apparatus will be described in detail. After the steps shown in FIGS. 2 to 5 described in the first embodiment, the wafer to which the reaction product 26 is attached is placed on the wafer processing apparatus table, and the vacuum is turned on as shown in FIG. 19 The exhaust pipe j and the jade lice tube 4 exhaust the inside of the container j to make it vacuum, and then stop exhausting. Be polite. Next, open the 脉冲 pulse valve 6 for hydrofluoric acid and supply hydrofluoric acid (HF) to the container! in. At this time, the time until the reaction product 26 begins to erode & inferior, and the percentage is reduced tl --------- * -------- Order ------ --- Line · (Please read the notes on the back * " before filling out this page) 522464 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (22) Within t, open the hydrofluoric acid gas Pulse valve 6 while holding hydrofluoric acid gas (1st time). As shown in Fig. 19, when the hydrogen acid gas is supplied into the container 1, the inside of the container is not exhausted. By the container! Internal supply gas Acid gas The pressure in the container rises. -After supplying the hydrofluoric acid gas, the reaction product and the gas acid gas are reacted with each other to produce SiF4, h2O, and the reaction product% is selectively left for a while. Next, the exhaust pulse valve 9 is opened to exhaust the inside of the container within a proper time. At this time, the SiF4 and H2O generated in the container and the absorbed moisture are discharged to the outside of the container. After the container is evacuated within an appropriate time, the exhaust pulse valve 9 is closed. Thereafter, the pulse valve 6 for the hydrofluoric acid gas is opened, and the hydrofluoric acid gas is supplied (second time) to the container. Thereby, the remaining reaction product 26 can be selectively removed in the same manner as in the case of the nitrous acid gas etched at the i-th time. After that, the control unit 11 controls the opening and closing of the pulse valve 6 for hydrofluoric acid gas and the pulse valve 9 for exhaust gas, and repeats the above operations (steps) an appropriate number of times, thereby eliminating the need to actually etch the silicon oxide film 22 Then, the reaction product 26 adhering to the surface of the gate electrode 23 a can be removed to a nearly complete degree. In particular, as shown in Fig. 19, since the hydrofluoric acid gas is not exhausted, the pressure in the container becomes larger when the hydrofluoric acid gas is supplied than when the container is vented frequently. Higher. As a result, the supply of the reaction product during the first supply period of hydrofluoric acid gas can be promoted. 1 ^ ni ^ i ϋ n · ϋ ϋ 0 ΜΎ (Please read the precautions on the back before filling this page) Order --------- line j This paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) 22

312940A 522464 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (23) is effective to remove the reaction products, and with a small number of operation repetitions, the reaction products 26 are selectively Complete degree of removal. In addition, although the case where the exhaust pulse valve 9 is provided in the vacuum exhaust pipe 4 in the wafer processing apparatus has been described in detail, in addition to the exhaust pulse valve 9, a high-speed variable vacuum exhaust can also be used. An electrically conductive valve in the air pipe 4. Sixth Embodiment Below, in the sixth embodiment, a wafer processing apparatus capable of intermittently supplying a hydrofluoric acid gas and an additional gas while intermittently exhausting the gas in a container, and a semiconductor using the same The device manufacturing method is explained in detail. As shown in FIG. 20, the hydrofluoric acid gas supply pipe 5 of the wafer processing apparatus is provided with a pulse valve for hydrofluoric acid gas, and the addition gas supply pipe 7 is provided with a pulse valve 8 for adding gas. The vacuum exhaust pipe 4 is provided with an exhaust pulse valve 9. The control unit 11 controls the pulse valve 6 for hydrofluoric acid gas, the pulse valve 8 for added gas, and the pulse valve 9 for exhaust, and regularly supplies the hydrofluoric acid gas, the supply of the added gas and the inside of the container. exhaust. In other words, as shown in Fig. 21, no exhaust gas is supplied when the nitrogen acid gas or the additive gas is supplied to the container, and no hydrofluoric acid gas is supplied during the supply of the additive gas into the container. Next, a manufacturing method using the wafer processing apparatus will be described in detail. After the steps shown in FIG. 2 to FIG. 5 described in the first embodiment, the wafer with the reaction money 26 attached to the wafer is placed on the wafer. The paper size applies the Chinese National Standard (CNS). A4 specifications⑵Q X 297 ----

23 312940A ----------------- Order --------- line (Please read the precautions on the back before filling this page) 522464

V. Description of the invention (24) 24 units of the Ministry of Economic Affairs, the Intellectual Property Agency, and the Consumer Affairs Agency of the Bureau of Finance and Industry have printed 24 units. Next, as shown in Fig. 21, the container is carried out by the vacuum exhaust pipe 4! After exhausting the inside, it will be evacuated and stop exhausting. Next, the pulse valve 8 for adding gas is opened, and water vapor is supplied (jth time) to the container i. The pulse valve 6 for hydrofluoric acid gas is opened, and the hydrofluoric acid gas (HF) is supplied to the container j only for a predetermined time. The water vapor supplied into the container adheres to the surface of the reaction product% as shown in FIG. 22. Next, the time for the "thin hydrofluoric acid gas pulse _ 6" is longer than the time u before the reaction product 26 starts to etch, and shorter than the time t2 before the silicon oxide film 22 starts to etch. Acid gas (1st time). As shown in Figure 20, the supply of water vapor and the supply of wind lactic acid gas can increase the pressure in the container. As shown in Fig. 23, after the supplied chlorine acid gas and the reaction product react with each other to produce SiFrhO, the reaction product 26 is selectively engraved. As described in Section 21 ®, the inside of the container is not vented while water vapor and nitrogen acid gas are being supplied to the container. In addition, by supplying water vapor and hydrofluoric acid gas into the container, the pressure in the container can be increased. After supplying the hydrogen acid gas within a certain period of time, the pulse valve for the hydrofluoric acid gas is closed. Next, open the pulse valve 9 for exhaust, and exhaust the air into the rice maker only within an appropriate time. At this time, as shown in Fig. 24, SiF4, HA, and attached moisture generated in the container are discharged to the outside of the container 1. After the inside of the container is evacuated only at an appropriate time, the bleed pulse valve 9 is closed. _ Times, as shown in Figure 21, open the pulse valve 8 for adding gas, only this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public duplicate) ^ ------------

312940A :::: 441 ---- Order --------- line (Please read the precautions on the back before filling this page) 522464 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs (25 within a predetermined time 'supply water vapor (second time) to the container! After that, the pulse for adding gas is turned off. Next, m-fluoric acid ㈣㈣㈣ 6'_ and only within a predetermined time, hydrofluoric acid gas (HF) Supply (the second time) to the controller 1. This allows the remaining reaction product% to be selectively removed, as in the case of the last name of the gaseous acid gas. The control unit 11 'controls the switching of the pulse valve for adding gas, the pulse valve 6 for hydrofluoric acid gas and the pulse valve 9 for exhaust, and repeats the supply of the additive gas, the supply and exhaust of the hydrofluoric acid gas at appropriate times. After a series of operations (steps), as shown in FIG. 25, the reaction product 26 attached to the surface of the gate electrode 23 & can be almost completed without etching the substantial silicon oxide film 22. In particular, in this method, the hydrofluoric acid Before the gas is supplied into the container, water vapor is supplied. Therefore, as explained in the fourth embodiment, although the time until the reaction product starts to etch can be shortened, on the other hand, the time before the silicon oxide film starts to etch. The time is hardly changed. Therefore, even if the supply time of the primary hydrofluoric acid gas is the same (for example, t2), the actual remaining time T1 of the reaction product 26 becomes longer. In addition, as described in the fifth embodiment, generally During the supply of hydrofluoric acid gas and water vapor, the exhaust is not performed. Therefore, compared with the case where radon gas is often used in the container, the pressure in the container becomes higher when the additional gas and the hydrofluoric acid gas are supplied. This can promote the remaining time of the reaction product during the first supply period of the hydrofluoric acid gas, and accelerate the remaining rate. As described above, when the first supply of the hydrofluoric acid gas is performed, the actual reaction generation is increased. The etching time of the object, and the increase of the etching rate, even if the reverse --------- # 1¾ ------- 丨 order --------- line t (Please read first (Notes on the back, please fill out this page) Chinese National Standard (CNS) A4 size (210 x 297 mm) 25

312940A 522464 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (26) The number of repetition operations is small, and the reaction product 26 can also be selectively removed almost completely. In addition, after removing the reaction product, the silicon oxide film 24a as a masking material shown in Fig. 25 must be removed. At this time, the water vapor is supplied into the container first, and then the hydrofluoric acid gas is supplied. After the hydrofluoric acid gas is supplied, the water vapor is continuously supplied, whereby the etching rate of the silicon oxide film 24a can be increased. (Seventh embodiment) In the foregoing embodiment, a method for removing a reaction product attached to a gate electrode has been mainly described. Here, a description will be given of a method of removing a mask material when a gate electrode pattern is formed. First, after passing through the steps shown in FIG. 2 to FIG. 6 described in the first embodiment, the wafer 2 on which the rhenium oxide 24a as a masking material remains on the gate electrode 23a is accommodated in a wafer such as Inside the container 1 of the wafer processing apparatus shown in FIG. 1. Next, the hydrofluoric acid gas is supplied into the container 1. As shown in FIG. 26, by the contact between the hydrofluoric acid gas and the wafer 2, the hydrofluoric acid gas reacts with the silicon oxide film 24a, and the silicon oxide film 24a is etched. This etching process will be described in detail. As shown in FIG. 7, there is a time difference between the time t1 after the chlorofluoric acid is supplied into the container 1 and the time t2 until the etching reaction product 26 starts, and the time t2 until the etching (graph B) starts. T (t2-tl). That is, the silicon oxide film 24a will start to be etched earlier than the gate insulating film 22. The cause of this time difference T is estimated to be the following. In the case of Shixi oxide film 24a as a cover material, it is generally used by the CDV method. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297mm S) --- 珉 之 —

26 312940A ---------------- -Order --------- line (please read the precautions on the back before filling this page) 522464 A7 B7 V. Description of the invention (27) TEOS (Tetra-Ethyl-Ortho-Silicate-glass) oxide film. On the other hand, the gate insulating film 22 is a stone evening oxide film formed by thermally oxidizing the silicon substrate 21. (Please read the precautions on the back before filling this page.) As is generally known, TEOS oxide film is compared with stone oxide film formed by thermally oxidizing silicon substrate 21, such as OH-based impurities or moisture. The content of (H2O) is large. As before, when the silicon oxide film reacts with hydrofluoric acid gas, water (H2O) will be generated. When the reaction continues and the amount of water generated exceeds a certain amount, the etching rate will increase rapidly. The silicon oxide film 24a and the gate insulating film 22, which are used as a mask material, contain more impurities, so the reaction of the broken oxide film 2a will be faster than that of the gate insulating film 22. Therefore, as shown in FIG. 7, the time t when the hydrofluoric acid gas is supplied into the container 1 is set to be longer than the etching start time of the silicon oxide film 24 a and shorter than the etching start time of the gate insulating film 22. Therefore, it is not necessary to actually etch the gate insulating film 22, and it is possible to selectively etch only the silicon oxide film 24a. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs At this time, because the gate insulating film 22 is not left for a while, the notched portion under the idler electrode 23a will not be exposed. It should be noted that the time t1 and the time t2 in this case can preferably be obtained through experiments. In addition, when it is difficult to remove the silicon oxide film 24a with only one process, as described in the second embodiment, the process at the processing time t is repeatedly performed an appropriate number of times, without actually etching the gate insulating film 22, and the silicon can be oxidized. The film 24a is completely removed. In addition, the time before the broken oxide film 2 2 starts, and the paper size is set to the Chinese National Standard (CNS) A4 (210 x 297 mm) 27

312940A 522464 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

312940A A7 ____B7 _ 5. Explanation of the invention (28) 疋 is the upper limit t2 of the time for introducing the hydrofluoric acid gas. However, the above time can be used as an upper limit only when the stone oxidized film is etched to some extent, and the notch portion under the gate electrode is not exposed, and current leakage does not occur. In addition, the case where the silicon oxide film 24a as a masking material is selectively removed corresponding to the gate insulating film 22 has been described here, but the reaction product% generated when the gate electrode 23a is patterned is patterned The reaction start time t1 is shorter than the processing time when the silicon oxide film 24a is removed, and the reaction product 26 and the silicon hafnium oxide 24a can be removed at the same time. Thereby, the cleaning step after the gate electrode formation and the silicon oxide film removal step as a mask material can be performed in one step. In the above embodiment, as the gas for promoting the reaction, water vapor is taken as an example. However, in addition to water vapor, such as oxygen (〇2), ozone (〇3), nitrogen (N2), and helium Inert gases such as (He), neon (Ne), or ethanol gases such as CH3OH are also suitable. In addition, in each of the above embodiments, the case where the reaction product generated when the gate electrode is formed is removed is exemplified. In addition, for example, when the TE0S film is selectively etched corresponding to a thermal oxide film, Or corresponding to the TEOS membrane ', but for BPTEOS (B〇Γ〇— ph〇sph〇_ 丁 他 _

Ethyl-〇rth〇-Silicate-glass) film is selectively etched, or corresponding to PSG (Phospho-Silicate-Glass) 臈, while BpSG (B⑽ 一

Phospho _ Silicate-glass) film can also be selectively etched using the wafer processing apparatus described above. _glj0, can be started by the reaction of BPSG film and PSGj. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------- 28 i " id4 ------ -丨 Order --------- Line (Please read the precautions on the back ^ before filling this page) 522464 A7 ____B7 V. Description of Invention (29) Set as! And the supply time of the hydrofluoric acid gas is set to about] seconds or less, and it is confirmed that the corresponding selectivity of the PSG membrane is “selective.” The items described in this embodiment are only examples, not because of this. Limited. The present invention is not based on the above description, but is stated based on the scope of the patent application. It also includes all changes within the meaning and scope of the scope of the patent application. [Effects of the Invention] According to the method for manufacturing a semiconductor device according to one aspect of the present invention, since the etching gas supply step is performed longer than the i-th time and shorter than the second time, the etching in the second part starts. Until now, only the first! The wound was etched. As a result, it is not necessary to actually etch the second part, but it is possible to selectively etch the first part. More specifically, the time difference between the first start time and the second start time is preferably about 5 seconds or less. At this time, it is not necessary to etch, for example, the gate insulation, and it is possible to selectively only effect the reaction product. Remove. Ideally, a step of forming an insulating film on a semiconductor substrate; a step of forming a conductive field on the insulating film, and a step of forming an insulating film, including a step of forming a gate insulating film; and a step of forming a conductive field, including The step of forming the gate electrode portion on the gate insulating film; the first part, which is generated when the gate electrode portion is formed, contains a reaction product covering the surface of the gate insulating film and the surface of the gate electrode portion; the second part The gate insulating film is included in some parts. Because the etching gas contains hydrofluoric acid gas, it is not necessary to actually apply the remaining insulating film when removing the reaction products attached when forming the gate electrode portion. The reaction product can be selectively etched with 29 lines. The paper size is applicable to the Chinese National Standard (CNS) A4 size ⑵Qx 297 public meals) --------- 312940A 522464 A7 V. Description of the invention (3〇 It is also possible to selectively remove the reaction products. In addition, the wafer processing step is ideally provided with a reaction-promoting gas that shortens the start time before the etching gas supply step. The added gas supply step introduced into the container shortens the first start time by the reaction-promoting gas, and the etching time for the first part becomes longer. As a result, the processing time of the wafer processing step can be shortened. More preferably, in the wafer processing step, the additive gas supply step and the remaining gas supply step are performed alternately, whereby the second part can be left and the first part can be selectively removed surely. Above, in the wafer processing step, the addition of a gas supply step is continued after the etching gas supply step, so the engraving speed on the etching supply step can be increased to achieve the purpose of shortening the processing time of the wafer processing step. More desirably, the wafer processing step includes an exhaust step for performing exhaust in the container; and the exhaust step is not performed at least during the etching gas supply step, so compared with the case where the exhaust step is not performed normally, During the 步骤 supply step, the pressure in the container of Jiang Lin ’s Intellectual Property Bureau ’s employee property cooperative ’s printed knives will rise to two, and Part 1 is effectively etched. Ideally, it should be provided with a step of forming a conductive layer on the semiconductor gate insulation film to form a conductive layer; forming a conductive layer on the conductive layer in the shape of #A and continuing as a masking layer The step of masking the mask layer and forming a gate electrode by etching the conductive layer and the other layers; and after the blue electrode is formed on the closed electrode, removing the gate electrode The remaining mask layer on the electrode, w The wafer processing step includes the step of removing the mask layer. The first part contains the (CNS) A4 specification, and the second part contains the first 522464. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees ’Cooperative, Ltd. 31 A7 B7 V. Description of the Invention (31) In the etching gas supply step, the gas gas acid gas is used as the etching gas, so in this case In order to remove the mask layer used for patterning the gate electrode, it is not necessary to actually etch the gate insulating film, but the mask layer can be selectively etched, and the mask can be selectively masked. The layer is removed. Λ In addition, ideally, in the wafer processing step, the etching supply step is repeatedly performed. Even if the mask layer cannot be removed by one etching, the gate insulating film does not need to be etched by the repeated etching gas supply step. The cover is definitely removed. More desirably, the wafer processing step includes an exhaust step for exhausting the inside of the container, and by performing an etching supply step and an exhaust step alternately, in the etching gas supply step, the pressure in the container will rise, and The masking layer applies a valid finish. According to another aspect of the semiconductor device of the present invention, since the first part is selectively etched to the second part, the reaction product attached when the gate electrode is formed, for example, can be removed without actually having to gate the gate electrode. Insulation film is etched. In addition, the mask layer when the gate electrode is formed can be removed without actually etching the gate insulating film. As a result, deterioration of the electrical characteristics of the semiconductor device can be prevented. 2. In accordance with yet another form of the wafer processing apparatus of the present invention, the first part is engraved with ##, only the first part is carved with #, and the second part can be selectively carved without actually having to #engage the second part. 1 part is etched. Thereby, the reaction product attached when a gate electrode of a semiconductor device is formed, for example, is L β% 0 & '' '' '' gate y edge film does not need to be actually etched, and 312940A ϋ I ϋ ϋ ϋ H ϋ ϋ n (Zero I — ^ OJi w. ·. I ··· β · — I review (Please read the notes on the back before filling this page) 522464 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

312940A A7 B7 5. Description of the invention (32) Only the reaction product can be selectively removed, and the electrical characteristics of the semiconductor device can be prevented from being deteriorated. In particular, in this wafer processing step, when the time difference between the first start time and the second start time is less than about 5 seconds, the first portion can be selectively etched with certainty. Ideally, an additional gas supply unit for supplying a reaction promoting gas' to shorten the first start time in the container is provided, and the control unit includes a means for performing the reaction promoting gas in the container by the additional gas supply unit before the gas supply is performed. Due to the function, the first start time can be shortened by the reaction-promoting gas, and the etching time in the first part will increase. As a result, the processing time will be shortened, and the throughput of the wafer processing step can be improved. In addition, ideally, the control section includes a function of alternately performing an etching gas supply and a reaction-promoting gas supply, thereby repeatedly applying the etching to the i-th part, leaving the second part, and selectively selectively Portions are definitely removed. More desirably, the control unit also includes a function of performing a reaction to promote the supply of gas during the period of supplying the gas for etching, so that the etching speed at the time of applying the etching to the part ^ can be increased. Thereby, the processing time will be shortened, and the production capacity of the wafer processing apparatus can be improved. Ideally, an exhaust unit for exhausting the inside of the container should be provided, and the control unit should include a function to stop the operation of the exhaust unit at least during the execution of the etching gas supply. During the implementation of the gas supply, the pressure in the container will increase even more, and effective convergence can be applied to the first part. --- (Please read the notes on the back before filling out this page) 522464 Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Yin Fan 33 A7 V. Description of the Invention (33) According to the present invention, _ 甘 A 〇 / Afc Sunda shape The cleaning method after the formation of the evil gate electrode does not need to cut the gate insulating film, and the reaction products can be removed. ~ The upper gate electrode is formed at least from a film containing silicon element. By forming a gate electrode formed from a film with 3 broken elements, the reaction product will be generated. Second, A_ The main wound will become When silicon oxides are used to remove reaction sites and necessary materials by hydrofluoric acid gas, the reaction product can be reliably removed without removing the gate insulating film. In addition, it is characterized in that, ideally, the time for removing the reaction product by the hydrofluoric acid gas is 'the time when the cutting of the reaction product by the hydrogen acid gas is preferable' and the time when the cutting of the electrode insulation film is generated. During the reaction time difference, there is no need to cut the gate insulating film, and only the reaction product can be removed. A more ideal feature is that, by repeatedly setting the reaction time difference, the reaction is made of nitrogen fluoride gas to remove the money and borrow & while only the reaction product is reliably removed. Specifically, the gate electrode The formed semiconductor substrate is placed in a container, and the repeated setting of the reaction time difference is performed by repeatedly vacuuming the inside of the container and filling the hydrofluoric acid gas. It is characterized in that: ideally, it is better to set the set temperature when removing the reaction product by hydrofluoric acid gas to a temperature lower than 40 ^, so that the shortening of the reaction time difference will be controlled, and _ This makes it easier to remove the reaction product. The lower limit of the set temperature is preferably room temperature. [Simple description of pattern] Fig. 1 is a sectional view of a wafer processing apparatus according to a first embodiment of the present invention. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

312940A -------- Order --------- line (please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs like 464 34) FIG. 2 is a cross-sectional view of one of the steps in the method of manufacturing a semiconductor device according to the first embodiment of FIG. 1. Fig. 3 Gu; ^ ρ is a cross-sectional view of the steps performed after the steps of Fig. 2 in the first embodiment. Fig. 4 is swallowed, and \ k is not shown in the cross-sectional view of step 7 in the j-th embodiment after step 7 shown in Fig. 3. Fig. 5 is a cross-sectional view showing the steps performed after the steps shown in Fig. 4 in the first embodiment. Section ® shows a cross-sectional view of the steps performed after the steps shown in Fig. 5 in the first embodiment. Fig. 7 is a graph showing the respective cut-off amounts of the reaction product and the gate insulation plutonium in accordance with the elapsed time after the introduction of hydrofluoric acid gas into the valleyr in the first embodiment. Fig. 8 is an explanatory diagram of a method (cleaning method) for manufacturing a semiconductor device according to a second embodiment of the present invention. Fig. 9 is a cross-sectional view of a wafer processing apparatus according to a third embodiment of the present invention. Fig. 10 is a cross-sectional view showing one step of the method for manufacturing a semiconductor device according to the third embodiment. Fig. 11 is a diagram for explaining a processing method in the third embodiment. FIG. 12 is a cross-section of a wafer processing apparatus according to a fourth embodiment of the present invention. FIG. 13 is a diagram for explaining a processing method in the fourth embodiment. --------- ^ -------- Order —-------- Line (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 34

312940A 522464 A7 " '-------- --_ B7 V. Description of the invention (35) 図 — The garden is not. Fig. 14 is a first cross-sectional view showing the form of the reaction product when the reaction product is etched in the fourth embodiment. Fig. 15 is a second cross-sectional view showing the state when the reaction product is etched in the fourth embodiment. ΛFill in this page) Fig. 16 shows a third cross-sectional view of the form when the reaction product is etched in the fourth embodiment. Fig. 17 is a graph showing the respective cut-off amounts of the reaction product and the gate insulating film according to the elapsed time after the introduction of the chloric acid gas into the container when the water vapor is introduced in the fourth embodiment. FIG. 18 is a cross-section of a wafer processing apparatus according to a fifth embodiment of the present invention. FIG. 19 is a diagram for explaining a processing method in the fifth embodiment. FIG. 20 is a wafer processing apparatus according to a sixth embodiment of the present invention. Section pgl Printed by the Consumers' Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs. Figure 21 is a diagram for explaining the processing method in the sixth embodiment. Fig. 22 is a first cross-sectional view showing the state when the reaction product is etched in the sixth embodiment. Fig. 23 is a second cross-sectional view showing a state when the reaction product is etched in the sixth embodiment. Fig. 24 is a third cross-sectional view showing the state when the reaction product is etched in the sixth embodiment. This paper size applies to Chinese National Standard (CNS) A4 specification ⑵Q χ 297 meals. · 35 35312940A 522464 V. Description of the invention (36) 2 5 Figure gg One of the manufacturing methods of the semiconductor device of the sixth embodiment A cross-sectional view of a step ^ ^ township. Fig. 26 Fig. Mb shows a cross-sectional view of the top step of the method for manufacturing a semiconductor device according to the seventh embodiment of the present invention. Fig. 27-Fig. A cross-sectional view of the steps of the manufacturing method of the semiconductor device, which is not used in the past. The second and eighth picture display + the other cross-sectional view of one of the steps of the semiconductor device manufacturing method. Another cross-sectional view of one of the steps in the conventional method of manufacturing semiconductor devices. [Explanation of component symbols] 1 3 5 7 11 23a 25 ^ --------- (Please read the precautions on the back before filling This page) Container support Typhoon fluoric acid supply pipe Gas supply pipe 2 4 6-8 9 Wafer vacuum exhaust pipe Pulse valve exhaust pulse valve control unit 21 Substrate silicon oxide film 23 Polycrystalline silicon gate electrode 24a Oxide film mask Photoresist pattern 26 reaction Ministry of Economy was wise property office employees consumer cooperatives paper printing system of this scale applicable Chinese National Standard (CNS) A4 size (210 x 297 public complex) 36

312940A

Claims (1)

522464 z No. 90126550 Patent Application Amendment of Patent Scope (9 1 cars 1, •: a method for manufacturing semiconductor devices, used for the second month) has a predetermined / formed semiconductor on the substrate. ㈣: servings, as well as having the same gas as the previous one, enter the rod in the Rongqin and carry out the etching _ into the wafer processing boat for the pre-treatment process. In addition to the wafer processing steps, there are: Into the aforementioned = gas supply step for the last name in the device, using the gas guide part :: Γ # After the gas is introduced into the container, the first gas guide is used: 2 = as the first start time 'and the aforementioned When the neodymium is engraved, the gate will be etched from the inside to the beginning of the second part, so it is longer than the first time. The second time is the time it takes to perform the gas supply step. The start time is longer than the second start time. 2. Application: The manufacturing method of the semiconductor dress in item 1 of the Λ Lee scope, the employee welfare committee of the Central Standards Bureau of the Ministry of Economic Affairs prints the difference between the time when the first 1% of the brother and the second time is about 5 seconds . 3. A method for manufacturing a semiconductor device, such as the one or two items in the scope of patent application, wherein the method includes: a step of forming an insulating film on the semiconductor substrate; and forming a conductive region on the insulating film. The step of forming the insulating film includes a step of forming a gate insulating film, and a step of forming a gate insulating film. The standard is a yirir specification (21Gx29 ·) 1 312940A 522464. The step of forming the aforementioned conductive region includes the aforementioned inter-electrode insulation. On the film, a gate electrode portion is formed, and the first portion 'forms a reaction product that covers the surface of the inter-electrode insulating mold and the surface of the closed electrode portion when the gate electrode portion is formed, and the second portion includes The idle electrode insulating film, and the remaining gas includes a hydrofluoric acid gas. For example, the method for manufacturing a semiconductor device in the scope of the patent application item i or item 2, wherein the aforementioned wafer processing step is provided with: before performing the aforementioned _ use of the milk supply step 'will be used to promote the short reaction from the aforementioned ι to promote Before the introduction of the gas, Ma Ma Shou quoted the step of adding gas to the valley device as described in the patent application No. 4 of the semiconductor device. ^ ^ L ~ Yi Wan Wan Fa, 1, in the wafer processing steps described above, " _ Then the supply step of adding lice is described alternately. The gas supply step for etching is performed alternately. ^ 6 The Employee Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs printed a method for manufacturing a semiconductor device such as the scope of patent application No. 4, and it was' In the aforementioned wafer processing step, the aforementioned added gas supply + step is continued after the aforementioned gas supply step for etching is started. 7. For example, in the application of the scope of the patent application item 丨 or the semiconductor of the second item: installation: method Among them, the aforementioned wafer processing steps are provided with: ^ Internal exhaust function, the above-mentioned exhausting step of the container is not performed at least during the aforementioned gas quenching step. T, 6 Step This paper size applies the Chinese National Standard (CNS) A4 regulations (21 × 297 public love) 312940A 2 Method: The patent covers the manufacturing method of the semiconductor device of item i or item 2-"The method is provided with a method of: · on the semiconductor substrate, a dielectric film", "," and an edge film to form a conductive layer. Steps: forming a step as a mask layer on the conductive layer; performing steps of forming a mask electrode on the conductive layer to form a gate electrode; and After forming the gate electrode, the mask layer is removed from the gate electrode, and the wafer processing step includes the step of removing the mask layer, and the first part includes the mask. The cover layer, in addition to the second part, includes the aforementioned gate insulating film, and in the step of supplying the etching gas just mentioned, a hydrofluoric acid gas is supplied as the etching gas. In the manufacturing method of the device, in the above-mentioned round processing step, the aforementioned etching gas supply step is repeated. The Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs prints semiconductor devices such as the scope of the patent application for 9 items. The manufacturing method includes a wafer processing step, which includes an exhaust step for performing exhaust in the container, and a gas supply step and the exhaust step are alternately performed. 11. A wafer processing device, which uses The etching gas is used for the first part having predetermined etching characteristics formed on the wafer and having a paper size corresponding to the predetermined etching. The Chinese standard (CNS) M specification ⑽x 297 ^) 3 312940A 522464 wyear> dagger The characteristics of the neodymium-etched characteristics with different characteristics are as follows: predetermined processing of the knife into the wafer, and the capacity of the wafer to accept the fate of the wafer; the aforementioned etching gas is supplied to the a body supply unit; The etching gas is used to control the supply of the etching gas. The control unit has the following functions before the container: If the #lithography gas is introduced, the description is as follows: The time from the inside of the container to the first etch before the beginning of the wound is etched, and the gas is introduced into the above-mentioned volume, and the time is started, and the time from the first _h to the start of the second part of the etching is done. For the second start pe ^ aB, the etching gas is supplied to the container from the neodymium engraving gas supply unit only in a time shorter than the first start N · time and shorter than the second start time. Of supply. 12. As for the wafer processing device in the u range of the patent application, the time difference between the first start time and the second start time is about 5 seconds or less. Printed clothing by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs 13. If the wafer processing device of the U or 12 items of the scope of patent application is applied, the device is provided with a reaction-promoting gas supply to shorten the i-th start time To the additive gas supply unit in the container, the control unit has the following functions: Before supplying the etching gas, the supply of the etching gas by the additive gas supply unit to the container is performed. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 4 312940A 522464 14. If the wafer control unit in the scope of patent application No. 13 is provided with an alternate solid rod, ‘where’ is described, it has the function of promoting gas supply for etching. Lfeeding, feeding and reversing 15. For example, the wafer section control section of the scope of application for patent No. 13 includes the function of supplying the gas for gas engraving. Yibei Describe 16. If the nth item of the scope of the patent application, the device has the function to prevent the front == and the aforementioned control unit at least contains the function of removing ticks every __ to stop the action of the aforementioned exhaust unit . 'Do n’t stop the etching gas supply at 17: f after the gate electrode is formed. The cleaning method is characterized in that: the semiconductor ^ upper dielectric gate edge film' is etched using a mask. After the gate electrode, the reaction product produced by the previous engraving is removed by hydrofluoric acid gas. 18. The cleaning method after the formation of the idler electrode in item 17 of the application for a patent, wherein: the aforementioned gate electrode is formed at least by a film including a stone wafer. Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs. For example, please ask for the method of cleaning the gate electrode after the formation of the 17th or 18th patent. It is performed within the reaction time difference between the time when the reaction product is cut by the hydrofluoric acid gas and the time when the gate insulating film is cut. 2 0 The method of cleaning the gate electrode after the formation of item 19 of the patent scope of the patent, of which: by repeatedly setting the aforementioned reaction time difference, the previous Chinese paper standard (CNS) A4 specification (210 x 297 public love) 5 312940A 522464 I;: * ^ r The argon fluoride acid gas removes the aforementioned reaction products. Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs 2 1 · If the gate electrode is cleaned after the application of the patent application No. 20, wherein the semiconductor substrate after the gate electrode formation is placed in a container, the aforementioned The repetition of the reaction time difference is to repeatedly perform the step of making the inside of the container into a vacuum and the step of filling the aforementioned hydrofluoric acid gas. 22. According to the method for cleaning the gate electrode after the formation of the 17th or 18th of the scope of the patent application, wherein the set temperature when removing the reaction product formed by the aforementioned hydrofluoric acid gas is set to A temperature lower than 40. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 6 312940A