Pattern forming material and pattern forming method

Abstract: A pattern forming material includes a binary copolymer represented by the following general formula or a ternary or higher copolymer obtained by further polymerizing the binary copolymer with another group: wherein R 1 indicates a hydrogen atom or an alkyl group; R 2 and R 3 independently indicate a hydrogen atom, an alkyl group, a phenyl group or an alkenyl group or together indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl group or a cyclic alkenyl group having a phenyl group; R 4 indicates a hydrogen atom or an alkyl group; x satisfies a relationship of 0 < x < 1; and y satisfies a relationship of 0 < y < 1.

Description: The present invention relates to a fine-line pattern forming method for use in a manufacturing process for a semiconductor IC device and the like, and a material for forming a pattern used in the pattern forming method. In the manufacture of ICs, LSIs and the like, a pattern is conventionally formed through photolithography using UV, in which a light source with a shorter wavelength has become mainly used in accordance with refinement of a semiconductor device. Recently, a surface imaging process using dry development has been developed in order to increase the depth of focus and improve practical resolution in using a light source with a shorter wavelength. As an example of the surface imaging process, U.S. Patent No. 5,278,029 discloses a method in which, after selectively forming a polysiloxane film on the surface of a resist film of a resist material which can generate an acid through exposure, the resist film is dry etched by using the polysiloxane film as a mask, so as to form a resist pattern. Now, this conventional method of forming the resist pattern will be described with reference to Figures 2(a) through 2(d). In this method, a copolymer of 1,2,3,4-tetrahydronaphthyridinenimino-p-styrene sulfonate (NISS) and methyl methacrylate (MMA) is used as the resist material for generating an acid through exposure. First, as is shown in Figure 2(a), a resist film 201, which generates an acid through exposure, coated on a semiconductor substrate 200 is irradiated with a KrF excimer laser 204 by using a mask 203, and thus, the acid is generated in an exposed area 201a of the resist film 201. Owing to this acid, the exposed area 201a is changed to be hydrophilic, so that water in air can be easily adsorbed by the exposed area 201a. As a result, a thin water absorbing layer 205 is formed in the vicinity of the surface of the exposed area 201a as is shown in Figure 2(b). Next, when an alkoxysilane gas 206 is introduced onto the surface of the resist film 201, the acid generated on the surface of the exposed area 201a works as a catalyst, so that alkoxysilane is hydrolyzed and dehydrated. As a result, an oxide film 207 is formed on the surface of the exposed area 201a as is shown in Figure 2(c). Subsequently, when the resist film 201 is dry etched by RIE using O 2 plasma 208 by using the oxide film 207 as a mask, a fine-line resist pattern 209 is formed as is shown in Figure 2(d). This pattern forming method thus adopts a negative type lithography process for forming a resist pattern in an exposed area, in which the acid generated in the exposed area of the resist film is used as the catalyst for selectively forming the oxide film in the exposed area and the oxide film is used as a mask in the dry etching for forming the resist pattern. The negative type lithography process has the following problems in, for example, forming a contact hole for connecting multilayered interconnections of an IC: First, usage of a mask generally adopted in pattern exposure can cause the following problem: In the lithography for forming a contact hole, the aperture ratio of the mask is very high when the negative lithography process is used. Specifically, while a light shielding film against exposing light is formed merely in a portion corresponding to the contact hole on the mask, the light shielding film is removed and quartz of the mask substrate is bare in the other portion excluding the contact hole in order to transmit the exposing light. Since the area occupied by all the contact holes in the entire area of a semiconductor chip is generally very small, the proportion of the area occupied by the bare quartz to the area of the light shielding film on the mask becomes high, namely, the aperture ratio of the mask becomes high. When the aperture ratio of the mask is high, the effect of ambient dusts is increased. Specifically, dusts adhered to the light shielding film on the mask scarcely affect the process, but those adhered to the transparent portion of the mask change this portion into a light shielding portion. When the exposure is effected by using the mask to which dusts are thus adhered, a pattern defect is caused in the portion to which the dusts are adhered. In this manner, since the aperture ratio of the mask is high in the negative type lithography process, the process can be easily affected by dusts, resulting in easily decreasing the yield. Secondly, in the lithography process for forming a contact hole, a half-tone type mask can be used for the purpose of increasing the depth of focus. However, the effect of increasing the depth of focus can be attained merely in a positive type lithography but cannot be attained in the negative type lithography. Accordingly, in the formation of a contact hole, the depth of focus is smaller in the negative type process than in the positive type process. The occurrence of these first and second problems are not limited to the formation of a contact hole, but can be caused in the cases where a mask having a larger area of the transparent portion is used and where the depth of focus is desired to be increased. In view of the aforementioned conventional problems, the object of the invention is realizing a positive type surface imaging process replaceable with the negative type surface imaging process. The present invention provides a pattern forming material comprising a copolymer including a first group for generating an acid through irradiation with an energy beam and a second group having a basic property. The present invention further provides a pattern forming method comprising: a first step of forming a resist film by coating a semiconductor substrate with a pattern forming material including a copolymer having a first group for generating an acid through irradiation with an energy beam and a second group having a basic property; a second step of selectively irradiating said resist film with said energy beam by using a mask having a desired pattern, generating said acid in an exposed area on said resist film and neutralizing said generated acid with said second group; a third step of supplying metal alkoxide onto said resist film and forming a metal oxide film on a surface of an unexposed area on said resist film; and a fourth step of forming a resist pattern by dry-etching said resist film by using said metal oxide film as a mask. Preferred embodiments of the present invention are set forth in the claims. The pattern forming material of this invention comprises a copolymer including a first group for generating an acid through irradiation with an energy beam and a second group having a basic property. When the resist film formed out of the pattern forming material is selectively irradiated with the energy beam, the first group is dissolved into the acid in the exposed area on the resist film, so that the generated acid can be neutralized with the second group having the basic property, while the unexposed area on the resist film remains to be basic. Accordingly, merely the unexposed area on the resist film can selectively retain the basic property, resulting in realizing the positive type surface imaging process. The first group in the pattern forming material is preferably a group for generating sulfonic acid. In this case, owing to the strong acidic property of sulfonic acid, the exposed area on the resist film can be completely neutralized, while the unexposed area on the resist film remains to be basic. Accordingly, the unexposed area of the resist film can selectively retain the basic property. The copolymer in the pattern forming material is preferably a binary copolymer represented by the following general formula or a ternary or higher copolymer obtained by further polymerizing the binary copolymer with another group: wherein R 5 indicates a hydrogen atom or an alkyl group; R 6 and R 7 independently indicate a hydrogen atom, an alkyl group, a phenyl group or an alkenyl group, or together indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl group or a cyclic alkenyl group having a phenyl group; R 8 indicates a hydrogen atom or an alkyl group; x satisfies a relationship of 0 < x < 1; and y satisfies a relationship of 0 < y < 1. In this case, amine can exhibit its strong catalytic function in the formation of the metal oxide film in the unexposed area on the resist film, so that the unexposed area on the resist film can selectively retain the strong basic property. On the other hand, in the exposed area of the resist film, since sulfonic acid having a strong acidic property is generated, amine having a strong basic property can be completely neutralized. Accordingly, merely the unexposed area on the resist film can selectively retain the strong basic property. The pattern forming method of this invention comprises a first step of forming a resist film by coating a semiconductor substrate with a pattern forming material including a copolymer having a first group for generating an acid through irradiation with an energy beam and a second group having a basic property; a second step of selectively irradiating the resist film with the energy beam by using a mask having a desired pattern, generating the acid in an exposed area on the resist film and neutralizing the generated acid with the second group; a third step of supplying metal alkoxide onto the resist film and forming a metal oxide film on a surface of an unexposed area on the resist film; and a fourth step of forming a resist pattern by dry-etching the resist film by using the metal oxide film as a mask. According to the pattern forming method, through the irradiation of the resist film with the energy beam, the generated acid is neutralized with the second group having the basic property in the exposed area on the resist film, while the unexposed area on the resist film remains to be basic. When the metal alkoxide is supplied to the resist film, the metal oxide film cannot be formed in the exposed area because the exposed area on the resist film has been neutralized, but the metal oxide film is selectively formed in the unexposed area on the resist film. Accordingly, through the dry etching of the resist film using the metal oxide film as a mask, it is possible to form a fine-line positive type resist pattern having a satisfactory shape. Furthermore, according to the pattern forming method, the base works as a catalyst in the formation of the metal oxide film in the unexposed area on the resist film. Therefore, the speed for forming the metal oxide film can be improved, resulting in improving throughput. In the pattern forming method, the third step preferably includes a step of allowing the unexposed area on the resist film to adsorb water. In this case, since water is diffused into a deep portion from the surface of the unexposed area on the resist film, the metal oxide film formed in the unexposed area on the resist film can attain a large thickness. In the pattern forming method, the first group is preferably a group for generating sulfonic acid. In this case, owing to the strong acidic property of sulfonic acid, the exposed area on the resist film can be completely neutralized, while the unexposed area on the resist film retains the basic property. Therefore, the metal oxide film can be formed merely in the unexposed area on the resist film with high selectivity. Accordingly, it is possible to form a more fine-line positive resist pattern having a satisfactory shape. The copolymer used in the pattern forming method is preferably a binary copolymer represented by the following general formula or a ternary or higher copolymer obtained by further polymerizing the binary copolymer with another group: wherein R 5 indicates a hydrogen atom or an alkyl group; R 6 and R 7 independently indicate a hydrogen atom, an alkyl group, a phenyl group or an alkenyl group, or together indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl group or a cyclic alkenyl group having a phenyl group; R 8 indicates a hydrogen atom or an alkyl group; x satisfies a relationship of 0 < x < 1; and y satisfies a relationship of 0 < y < 1. In this case, in the unexposed area on the resist film, amine exhibits its strong catalytic function, and hence, the metal oxide film with a sufficient density can be formed. On the other hand, in the exposed area on the resist film, since sulfonic acid having a strong acidic property is generated, amine having a strong basic property can be completely neutralized. As a result, the selectivity in the dry etching is very high, and it is possible to form a more fine-line positive resist pattern having a satisfactory shape. Figures 1(a) through 1(d) are sectional views for showing procedures of a pattern forming method according to the invention; and Figures 2(a) through 2(d) are sectional views for showing procedures of a conventional pattern forming method. The present invention will be explained in detail by way of the following example and with reference to Figures 1(a) through 1(d). As a resist material, a copolymer represented by the following formula dissolved in diglyme is used. First, as is shown in Figure 1(a), the resist material is spin-coated on a semiconductor substrate 100 of silicon, and the semiconductor substrate 100 is annealed at a temperature of 90°C for 90 seconds, thereby forming a resist film 101 with a thickness of 1 µm. At this point, no peeling is observed, and the resultant resist film 101 has satisfactory adhesion. Then, by using a mask 103, the semiconductor substrate 100 is irradiated with a KrF excimer laser 104, i.e., an energy beam, thereby transferring a pattern of the mask 103 onto the resist film 101. In this manner, on the surface of an exposed area 101a of the resist film 101, 1,2,3,4-tetrahydronaphthyridinenimino-p-styrene sulfonate (NISS) is dissolved to generate sulfonic acid. A reaction caused through the exposure of the resist material is shown in the following reaction equation: An unexposed area 101b of the resist film 101 has a basic property owing to the function of an amino group in the above formula. On the other hand, in the exposed area 101a of the resist film 101, NISS in the above formula is dissolved into sulfonic acid having a strong acidic property, so that the basic property derived from the function of the amino group can be neutralized. In this case, since the unexposed area 101b has the strong basic property, water can be more easily adsorbed in the unexposed area 101b than in the exposed area 101a having been neutralized. Specifically, since the unexposed area 101b includes the group having the strong basic property, a hydrogen bond with water is strengthened, and water can be easily adsorbed. In contrast, in the exposed area 101a, a hydrogen bond with water is weakened by the neutralization, and water cannot be easily adsorbed. Next, as is shown in Figure 1(b), the. semiconductor substrate 100 is allowed to stand in air with a relative humidity of 95% at a temperature of 30°C for 30 minutes, thereby supplying water vapor 105 onto the surface of the resist film 101. In this manner, the water vapor 105 is adsorbed by the surface of the unexposed area 101b, which can easily adsorb water, and the adsorbed water is diffused into a deep portion, for example, at a depth of 100 nm from the surface of the unexposed area 101b of the resist film 101. Since the exposed area 101a has been neutralized, water cannot be easily adsorbed. Thus, a water adsorbing layer 106 is selectively formed in the unexposed area 101b. Then, as is shown in Figure 1(c), while retaining the semiconductor substrate 100 in the air with the relative humidity of 95% at a temperature of 30°C, vapor 107 of MTEOS, i.e., metal alkoxide, is sprayed onto the surface of the resist film 101 for 3 minutes, thereby selectively forming an oxide film 108 on the surface of the unexposed area 101b of the resist film 101. In this case, the base derived from the amino group works as a catalyst in the hydrolysis and dehydration of MTEOS, so that the oxide film 108 can be formed. Therefore, the oxide film 108 is formed merely in a portion where both the base serving as the catalyst and water are present. In the exposed area 101a of the resist film 101, since the amino group is neutralized by generated sulfonic acid and loses its function as the catalyst and water cannot be easily adsorbed, the oxide film cannot be formed. In contrast, in the unexposed area 101b of the resist film 101, the base serving as the catalyst is present and a sufficient amount of water has been adsorbed, the oxide film 108 can be formed. Then, as is shown in Figure 1(d), by using the oxide film 108 as a mask, the RIE using O 2 plasma is effected, thereby forming a resist pattern 110. The RIE using O 2 plasma is effected by using a parallel plate reactive ion etching system under conditions of a power of 900 W, a pressure of 0.7 Pa and a flow rate of 40 SCCM. Since the oxide film 108 is selectively formed in the unexposed area 101b alone to be used in the etching, the positive type resist pattern 101 having a vertical section can be formed in the unexposed area 101b. Furthermore, since the water vapor 105 is supplied to the resist film 101 in the procedure shown in Figure 1(b), water is diffused into the deep portion from the surface of the unexposed area 101b of the resist film 101, so that the oxide film 108 can be grown toward the inside of the resist film 101. As a result, the oxide film 108 can attain a large thickness. In addition, since MTEOS is supplied to the resist film 101 in the air with the relative humidity of 95% in the procedure shown in Figure 1(c), equilibrium of water can be retained so that the water having been adsorbed by the resist film 101 can be prevented from evaporating and that water can be supplied in a sufficient amount for the formation of the oxide film 108. As a result, the resultant oxide film 108 can attain a thickness sufficiently large for withstanding the RIE using O 2 plasma. After the supply of MTEOS, the resist film 101 can be allowed to stand in vacuum so as to evaporate alcohol included in the oxide film 108. Thus, the flow of the oxide film 108 can be avoided. In this manner, the resist film 101 of the resist material including a basic group is subjected to the pattern exposure. In the exposed area 101a, a strong acid is generated to neutralize the basic property of the exposed area 101a, and the oxide film 108 is selectively formed in the unexposed area 101b alone, so as to be used in etching the resist film 101. Accordingly, it is possible to form the positive type fine-line resist pattern 110 having a satisfactory shape. Also, since water is forcedly adsorbed in the unexposed area 101b before forming the oxide film 108, the resultant oxide film 108 can attain a large thickness required for the dry development by the RIE using O 2 plasma. In the above example, the copolymer represented by the above formula includes the amino group as the basic group. However, the basic group is not limited to the amino group but can be any group having a basic property. Furthermore, MTEOS was used in the above example, but MTEOS can be replaced with any other metal alkoxide in a gas or liquid phase such as Si(OCH 3 ) 4 (tetramethoxysilane), Si(OC 2 H 5 ) 4 (tetraethoxysilane), Ti(OC 2 H 5 ) 4 , Ge(OC 2 H 5 ) 4 , Al(OC 2 H 5 ) 3 , and Zr(OC 2 H 5 ) 3 . Also, the dry development was effected by the RIE using O 2 plasma in this example, but ECR (electron cyclotron resonance etching) using O 2 plasma is adoptable instead. Moreover, a light source for the exposure was the KrF excimer laser in this example, but an i-line, an ArF excimer laser, EB or X-rays can be used. Furthermore, in the procedure for diffusing water in the surface of the unexposed area 101b of the resist film 101 in this example, the semiconductor substrate 100 was allowed to stand in the water vapor, but water in a liquid phase can be supplied to the resist film 101 on the semiconductor substrate 100 instead. However, water can be more rapidly diffused and the thickness of the oxide film 108 can be more increased when the water is supplied in a gas phase than in a liquid phase, and hence, water is preferably supplied in a gas phase. In the above example, the copolymer represented by the above formula was used as the resist material. However, for example, a group for generating sulfonic acid represented by any of the following formulae can be used as the sulfonic acid generating group. Also, the sulfonic acid generating group can be appropriately replaced with a group having a strong acidic property. Furthermore, the copolymer used in the example can be replaced with another ternary or higher polymer obtained by further polymerizing the aforementioned binary polymer with a compound represented by one of the following formulae:

Claims: A pattern forming material comprising a copolymer including a first group for generating an acid through irradiation with an energy beam and a second group having a basic property. The pattern forming material of Claim 1, wherein said first group is a group for generating sulfonic acid. The pattern forming material of Claim 1, wherein said copolymer is a binary copolymer represented by the following general formula or a ternary or higher copolymer obtained by further polymerizing said binary copolymer with another group: wherein R 5 indicates a hydrogen atom or an alkyl group; R 6 and R 7 independently indicate a hydrogen atom, an alkyl group, a phenyl group or an alkenyl group, or together indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl group or a cyclic alkenyl group having a phenyl group; R 8 indicates a hydrogen atom or an alkyl group; x satisfies a relationship of 0 < x < 1; and y satisfies a relationship of 0 < y < 1. A pattern forming method comprising: a first step of forming a resist film by coating a semiconductor substrate with a pattern forming material including a copolymer having a first group for generating an acid through irradiation with an energy beam and a second group having a basic property; a second step of selectively irradiating said resist film with said energy beam by using a mask having a desired pattern, generating said acid in an exposed area on said resist film and neutralizing said generated acid with said second group; a third step of supplying metal alkoxide onto said resist film and forming a metal oxide film on a surface of an unexposed area on said resist film; and a fourth step of forming a resist pattern by dry-etching said resist film by using said metal oxide film as a mask. The pattern forming method of Claim 4, wherein said third step includes a step of allowing said unexposed area on said resist film to adsorb water. The pattern forming method of Claim 4, wherein said first group is a group for generating sulfonic acid. The pattern forming method of Claim 4, wherein said copolymer is a binary copolymer represented by the following general formula or a ternary or higher copolymer obtained by further polymerizing said binary copolymer with another group: wherein R 5 indicates a hydrogen atom or an alkyl group; R 6 and R 7 independently indicate a hydrogen atom, an alkyl group, a phenyl group or an alkenyl group, or together indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl group or a cyclic alkenyl group having a phenyl group; R 8 indicates a hydrogen atom or an alkyl group; x satisfies a relationship of 0 < x < 1; and y satisfies a relationship of 0 < y < 1.

Inventors: ENDO MASAYUKI, MATSUO TAKAHIRO, SHIRAI MASAMITSU, TSUNOOKA MASAHIRO, ENDO, MASAYUKI, MATSUO, TAKAHIRO, SHIRAI, MASAMITSU, TSUNOOKA, MASAHIRO
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1997
Main classification: G03F7
IPC codes: G03F7