TWI299530B - - Google Patents

Description

1299530 V. INSTRUCTIONS INSTRUCTIONS (1) The method for forming a metal halide of 1 m:::, in particular, the method of removing the residual telluride telluride in the process of the right-side telluride. Tingda's metal M0S electricity is the body's operation speed and performance, and the common I ristance) ^ ^^^ Contact application - "first on the dream crystal plating - layer metal film The heat treatment produces a diterpene petrochemical having a suitable energy resistance height and uniformity. PtSi and Pdji are the earliest applications for integrated circuit components, which are used to reduce the resistance of aluminum alloy metal contact windows and to act as diffusion between aluminum and aluminum. In the early 1980s, about 1 line wide component generations, a variety of temperature metal halides, such as M〇Si2, TiS,

TaS is used by different companies in the US and Japan. In the current 0.25 /in generation, almost all TiSi2 is used. To 0.18 and smaller line width generation components, TiSi2, C〇SiylNiSi compete. Referring to Figures la to Le, Figures ia through 16 are conventional methods of forming metal halides. Referring to Figure la, first, a semiconductor substrate 1 is provided, and an insulating structure may be formed on the semiconductor substrate 101 to isolate An active region, such as a L0C0S or a shallow trench isolation region (not shown), etc. A pad layer 102, a conductive layer 1〇3, and a patterned photoresist 1〇4 are sequentially formed on the semiconductor substrate 1〇1. The patterned photoresist 104 is a mask etching conductive layer 1〇3 to form a gate 1〇3a, and then the patterned photoresist 104 is removed. The semiconductor substrate 1〇1 is, for example, 矽0503-7727TWf(N); TSMC2001- 1569 ; Claire.ptd Page 5 1 1299530 :, Description of the invention (2) ' ' ' ------ Substrate; underlayer 02 is, for example, an oxide layer; conductive layer 丨〇 3 is, for example, a multi-layer. y Please refer to the figure lb for compliance on the semiconductor substrate ι〇ι formed with gate i〇3a An insulating layer 丨〇5 is formed, and the insulating layer 丨05 is etched by a non-isotropic dry etching in a subsequent step to form a spacer: wherein the insulating layer 1 〇5 is, for example, tantalum nitride. Referring to FIG. 1c, the insulating layer 105 is etched by an isotropic dry etching to form the spacers 1〇5& and then, the semiconductor substrate is formed with the 9 closed-poles 103a and the gaps 105a. Forming a two metal layer 106 and a barrier layer 107 in sequence on the first layer, and then performing a tempering step on the semiconductor substrate 1〇1, wherein the metal layer 1〇6 is, for example, a cobalt metal layer (c〇); The layer 107 is, for example, a titanium-containing metal layer (Ti) or a titanium nitride layer (TiN), and the barrier layer 1 〇 7 has a function of preventing the metal layer 丨〇 6 from being oxidized in the tempering step. After the tempering step, the metal compound layer 108 is formed on the surface of the semiconductor substrate 101 and the gate electrode 103a which are in contact with the metal layer 1?6; at the same time, a residual metal layer is formed on the surface of the spacer 105a. 1 〇9 'Residual metal layer 1 〇9 is produced when metal compound 丨〇8 is formed The remaining residue must be removed. Among them, the metal compound layer 108 is a metal halide, such as a cobalt dioxide "heart" layer; the residual metal layer 109 is, for example, cobalt (c), cobalt oxide (c〇). 0), cobalt dioxide (C〇2 03 ) or cobalt trioxide (c〇3〇4), etc. Next, 'the cleaning step of the semiconductor substrate ιοί formed with the metal compound 需 is required' to remove the residual metal layer 丨〇9 And the metal layer 106 and the isolation layer 1〇7 remaining after the reaction.

0503-772711Vf(N) ; TSMC2001-1569 ; Claire.ptd Page 6 1299530 V. INSTRUCTIONS (3) RCA standard cleaning method (rca S tandard C 1 ea η ) is a kind of cleaning combined with SPM, DHF, APM and HPM. The law, developed and used in 1965, is still the most common wet cleaning method. The composition of SPM is H2S04 and Sapporo 2 'for the removal of organic pollutants, the reaction temperature is about 摄 丨 丨 丨 〇 ; ;; HF or diluted HF (DHF) is mainly used for etching oxide film (Si 1 icon oxide ) 'The reaction temperature is about 2 〇 25 ° C; the composition of αρμ is Ν 0 0 Η, Η 2 〇 2 and I 〇, used for water testing and surface erosion, in order to remove the particles 'reaction temperature about 3 摄 ° ~ 80 degrees; the constituents of bismuth are HC1, & 〇2 and Hg 0 ' are mainly used to remove metal contaminants, the reaction temperature is about 65 to 85 degrees Celsius. 0. Clean technology is used to remove various pollutants on the surface of the wafer. , generally has the characteristics of south oxidation and microparticle removal; high oxidation ability can oxidize metal and dissolve in clean solution, and can oxidize organic matter to c〇2 and 40, such as SPM and ΗΡΜ cleaning method have this function; ΑΡΜ can make the solution alkaline and produce a 刻# engraving effect to remove the particles. SPM, ηρμ, "Μ can achieve a high degree of cleansing, but it is necessary to use a large amount of chemicals and ultrapure water, and achieve the effect at high temperatures. The RCA method is mainly for the cleaning process of the front-end process design. At that time, the system scale and environmental safety requirements could not be compared with the current semiconductor industry. Therefore, under the demand for more precise wafer process development, it is urgently needed. The development of a new beta wash method to simplify the multiple steps required for traditional cleaning methods, and then J: the use of chemicals and pure water 4, in line with environmental management and the economic efficiency of wafer production. ΑΡΜAlthough the solution can be verified and micro-etching effect is generated to remove micro

0503-7727TlVf(N);TSMC200M569;Claire.ptd Page 7 1299530 V. INSTRUCTIONS (4) Particles 'However, during the cleaning process, the ammonium hydroxide (NH4〇H) component of APM will interact with the semiconductor substrate 101 and the gate. The reaction of the germanium component in 1〇3& causes the metal germanide on the surface of the semiconductor substrate 110 and the gate 103a to be eroded to cause voids, resulting in an increase in the resistance of the gate 103a, and the resistance of the gate 1〇3a. Elevation will slow down the operation of the transistor, as shown in Figure 16. / In view of the above, it is an object of the present invention to provide a method for forming a metal telluride and to remove a residual metal layer on a gate and a semiconductor substrate during the process without increasing the gate resistance. The operation speed of the transistor is not affected. In accordance with the above objects, the present invention provides a method of forming a metal ruthenium, comprising the steps of: providing a semiconductor substrate having a polysilicon gate on the semiconductor substrate, forming a metal layer on the surface of the polysilicon gate and the surface of the semiconductor substrate, and performing a semiconductor layer on the semiconductor substrate The tempering treatment is performed to react the semiconductor substrate with the polysilicon gate and the metal layer to form a metal halide; the semiconductor substrate is washed with an aqueous hydrogen peroxide solution to remove the unreacted metal layer; and the semiconductor substrate is washed with a cleaning solution containing phosphoric acid. In accordance with the above objects, the present invention further provides a method of forming a metal telluride comprising the steps of: providing a semiconductor substrate having a polysilicon gate formed thereon, wherein the polysilicon gate has a spacer; and the semiconductor substrate and the polysilicon gate Forming a metal layer and a barrier layer on the surface in sequence; tempering the semiconductor substrate to react the semiconductor substrate with the polysilicon gate and the metal layer to form a metal halide; immersing the semiconductor substrate in a hydrogen peroxide solution for cleaning To remove the insulating layer and the metal layer; and immerse the semiconductor substrate in a mixed solution containing phosphoric acid, nitric acid and acetic acid.

1299530 V Description of invention (5) Washing. According to the above object, the present invention further provides a method for forming a metal telluride, which comprises the steps of: providing a germanium substrate having a polycrystalline silicon gate formed on the germanium substrate; the polycrystalline germanium gate has a spacer, wherein the polycrystalline germanium gate Formed by a polycrystalline stone material; a metal layer and an oxidation barrier layer are sequentially formed on the surface of the germanium substrate and the polysilicon gate; the stone substrate is tempered to make the stone substrate and the polysilicon gate Forming a metal telluride, wherein a residual metal telluride is formed on the spacer of the polycrystalline silicon gate; the germanium substrate is immersed in an aqueous solution of hydrogen peroxide to remove the oxide barrier layer and the unreacted metal layer

And immersing the Shixia substrate in a mixed solution of phosphoric acid, nitric acid and acetic acid to remove the residual metal cerium compound.

According to the above object, the present invention further provides a method for forming a metal telluride, comprising the steps of: providing a germanium substrate having a polycrystalline whisker formed on the germanium substrate; wherein a sidewall of the polysilicon gate is formed with a spacer Forming a cobalt metal layer and a titanium-containing metal layer on the substrate and the polysilicon gate surface in sequence, and tempering the germanium substrate to form a cobalt dioxide layer on the surface of the germanium substrate and the polysilicon gate. A cobalt oxide layer is formed on the surface of the spacer; the ruthenium substrate is immersed in an aqueous solution of hydrogen peroxide to remove the titanium-containing metal layer and the unreacted cobalt metal layer; and the ruthenium substrate is immersed in phosphoric acid · nitric acid: acetic acid = 70 : 10 : 2 The mixed solution of -3 was washed to remove the cobalt oxide layer. EXAMPLES: Please refer to Figures 2a to 2f, and Figures 2 & 2 to 2 are a conventional method for forming metal halides. Please refer to Figure 2a. First, provide a semiconductor substrate 2〇1, semi-conductive.

1299530 V. INSTRUCTIONS (6) An insulating structure can be formed on the bulk substrate 2 0 1 to isolate the active region, such as L0C0S or shallow trench isolation regions (not shown). A pad layer 202, a conductive layer 203 and a patterned photoresist 2〇4 are sequentially formed on the semiconductor substrate 2〇1. The conductive layer 202 is etched with the patterned photoresist 204 as a mask to form the gate 2〇3a, and then the patterned photoresist 204 is removed. Wherein, the semiconductor substrate 2 is, for example, a germanium substrate; the pad layer 2 0 2 is, for example, an oxide layer; and the conductive layer 2 3 is, for example, a polycrystalline layer. Referring to FIG. 2b, the semiconductor substrate 2 having the gate 2〇3a is formed (n is compliant to form an insulating layer 205, and the insulating layer is formed by anisotropic drying in a subsequent step). The spacer is formed to form a spacer. The insulating layer 200 is, for example, a nitride nitride. Please refer to FIG. 2c to engrave the insulating layer 250 by an isotropic dry etching method. After the spacers 2 〇 5 a are formed, then, a metal layer 206 and a barrier layer 207 are formed on the semiconductor substrate 2 on which the gate 20 3a and the spacers 20 5a are formed (n sequentially), and then Oxygen tempering the semiconductor substrate 201. The metal layer 2〇6 is, for example, a cobalt metal layer (c〇): the barrier layer 207 is, for example, a titanium-containing metal layer (τ i) or a titanium nitride layer (τ丨N) The barrier layer 207 has a function of preventing the metal layer 206 from being oxidized in the tempering step. Referring to FIG. 2d, after performing the tempering step, the surface of the semiconductor substrate 201 and the gate electrode 203a in contact with the metal layer 2〇6 A metal compound layer 208 is formed thereon; at the same time, a residual metal layer 209 is also formed on the surface of the spacer 205a. Metal-based layer 209 is formed in excess residue of metal compound generated 208, and therefore must be cleared wherein the metal compound layer 208 that is a metal silicide such as cobalt silicide di (c〇Sd layer; Residual

0503-7727TWf(N) ; TSMC2001-1569 ; Claire.ptd Page 10 1299530 V. Inventive Note (7) ' " Metal layer 109 is, for example, cobalt (c〇), cobalt oxide (c〇〇), trioxide Cobalt (C 〇 2 〇 3 ) or the beginning of tetraoxide (C 〇 3 〇 4 ). Next, a cleaning step of the semiconductor substrate 20 i on which the metal compound 208 is formed is performed to remove the residual metal layer 2 〇 9 and the metal layer 206 and the isolation layer 2 〇 7 remaining after the reaction. The semiconductor substrate 201 on which the metal compound 2〇8 and the residual metal layer 209 are formed is placed in a hydrogen peroxide cleaning bath containing a hydrogen peroxide (H2〇2) solution having a temperature of about 2 Torr to 5 Torr. The aqueous hydrogen peroxide solution removes the remaining metal layer 206 and the barrier layer 207 after the reaction, and then the semiconductor substrate 2?1 having the residual metal layer 209 is taken out and placed in a deionized water cleaning bath for cleaning. Referring to FIG. 2e, after the semiconductor substrate 2〇1 is taken out from a deionized water cleaning bath, the semiconductor substrate 2〇1 still having the residual metal layer 20 9 is placed in a cleaning bath containing a mixed solution, and the mixed solution is washed. The temperature of the washing tank is about 65 to 85 degrees Celsius, and in the following description, the mixed solution is referred to as a solution. Solution A consists of several kinds of solutions, which can effectively remove metal oxide residues. The most important component is phosphoric acid (H3P〇4). The other components are nitric acid (hn〇3), acetic acid (CHgCOOH) and deionized water (j). i water), the composition ratio is about phosphoric acid · nitric acid: acetic acid = 7 〇: 1 〇: 2 - 3; wherein the concentration of linonic acid is 60~80 wt% 'the optimum concentration is 73 〜3 wt%; nitric acid The concentration is 3~5~1:%; the concentration of acetic acid is 3~5~1:%. The core solution can effectively remove the residual metal layer 209' and the metal layer 2?6 and the barrier layer 2?7 which are not completely removed can also be removed. After cleaning with a solution, the semiconductor substrate without residue is taken out from the A solution cleaning bath and placed in another deionized water rinse.

0503-7727TWf(N) ; TSMC2001-1569 ; Claire.ptd Page 11 1299530

In the bath = wash. The finished semiconductor substrate 201 is shown in Figure 2f. And the components of the closed tf solution and the & solution do not react with the composition of the semiconductor substrate 2, and therefore do not be raised on the surface of the gate 2〇3a; the resistance of the in1 pole 2〇38 does not Sharply increased. When the method of the present invention is formed by the metal lithium, 丄', 、, 、, 夕 a 矽, compared with the conventional RCA standard: the resistance of all the m-poles can be reduced by about 3 〇% or so; formed by the main / secret, when the formation of polycrystalline stone, compared to the conventional practice is not allowed to β washing method, a 'gate resistance can be reduced by about 丨〇%. w ^ This, compared to the method of forming a metal telluride, the operation speed of the invention is not seriously affected by the sharp increase in the gate resistance. It is known that the commonly used RCA standard cleaning method has the ApM and HpM cleaning method = although the composition of the two components has the composition of the sputum 2, but the reaction temperature of the ApM is about 8% to 80 degrees, and the reaction temperature of the HPM is about 65 to 85 degrees Celsius. Degree, h2〇2 is easily evaporated at higher=two degrees, so I% of the composition of ApM and Qing has a limited function. Although the present invention has been disclosed in the above preferred embodiments, the present invention is not intended to be limited to the present invention, and the present invention can be modified and retouched without departing from the spirit and scope of the present invention. The scope of protection is subject to the definition of the scope of the patent application attached.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, and advantages of the present invention will become more apparent and understood. As follows: Figures 1a through 1e are conventional methods for forming metal ceramsite. 2a to 2f are diagrams of the method of forming a metal halide of the present invention. DESCRIPTION OF REFERENCE NUMERALS 101, 201~ semiconductor substrate; 102, 202~pad layer; 103, 203~ conductive layer; 1 0 3 a, 2 0 3 a ~ gate; 104, 204~ patterned photoresist; 2 0 5 ~ insulating layer; 105a, 205a~ spacer; 106, 206~ metal layer; 107, 207~ barrier layer; 108, 108a, 208~ metal compound; 109, 209~ residual metal layer.

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Claims (1)

1299530 Case No. 91112080 VI. Patent Application Scope I A method for forming a metal ruthenium, comprising the following: providing a semiconductor substrate having a polycrystalline and closed polypole and a polyphenylene gate and a surface of the semiconductor substrate a metal layer; the half of the polycrystalline shredder will be a half metal layer, which will be half of the 2 · as claimed, wherein the 3 · as claimed, wherein the 4. as claimed, wherein the 5. The method of the method of washing the base of the conductor and the base of the double conductor of the gold conductor base, please patent the semiconductor base, and the metal layer of the patent is tempered by the patented semiconductor, and the semiconductor is tempered to make the semiconductor The substrate reacts with the genus layer to form a metal ruthenium; it is washed with an aqueous hydrogen peroxide solution to remove the unreacted aqueous solution excluding ammonia water; and washed with a cleaning solution containing phosphoric acid. Further, the metal oxide forming layer described in the first item further includes a gate oxide layer. The starting metal layer forming the metal telluride as described in Item 1. The material forming the metal telluride described in the first item is the beginning of the fragmentation. The square bottom forming the metal telluride described in item 1 is immersed in the aqueous solution of hydrogen peroxide. 6. If the application is as follows. 7. If the application is as stated in the first item of claim 1, The side of the metal lithium is formed: the bottom of the 2 is washed by immersing in the phosphoric acid solution. : 2 = The metal halide forming compound described in Item 1 further comprises a retortic acid solution and an acetic acid solution. ^The method of forming the metal lithium as described in the m item * The group of the acid solution, the nitric acid solution and the acetic acid solution 1299530 θ correction proportional to disc acid: acid · acetic acid = 7 〇 · · 1 〇 · · 2 _ 3. 9. The method of forming a metal halide according to claim 1, wherein the semiconductor substrate is immersed in an aqueous hydrogen peroxide solution and further comprises the step of washing the semiconductor substrate with deionized water. 10. The method of forming a metal halide according to claim 1, wherein the semiconductor substrate is immersed in an aqueous hydrogen peroxide solution and further comprises the step of washing the semiconductor substrate with deionized water. 11 . A method of forming a metal ruthenium, comprising the steps of: a semiconductor substrate having a polysilicon gate formed thereon, wherein the polysilicon gate has a spacer; y is on the semiconductor substrate and Forming a metal layer and a barrier layer on the surface of the polysilicon gate sequentially; tempering the semiconductor substrate to react the semiconductor substrate with the polysilicon gate to form a metal halide; The semiconductor substrate is immersed in an aqueous hydrogen peroxide solution to remove the barrier layer and the metal layer, wherein the aqueous hydrogen peroxide solution does not include ammonia water; and the semiconductor substrate is immersed in a mixed solution containing phosphoric acid, nitric acid and acetic acid for cleaning. The method of forming a metal halide according to the above-mentioned claim, wherein the material of the spacer is tantalum nitride. 13. A method of forming a metal halide as described in claim n, wherein the metal layer is a cobalt metal layer. The method of forming a metal halide according to the invention of claim 11, wherein the barrier layer is a titanium-containing metal. 1299530 Amendment 1 5 A method of forming a metal ruthenium as described in the scope of claim 4, wherein the barrier layer is a nitrided titanium-containing metal layer. The method of forming a metal telluride as described in the first aspect of the patent application, wherein the metal halide is cobalt telluride. The method of forming a metal halide as described in claim 11 wherein the composition ratio of the mixed solution is phosphoric acid: nitric acid: acetic acid = 7 〇 : 10 : 2-3 . The method of forming a metal telluride as described in the scope of the patent application, wherein the immersing the semiconductor substrate in an aqueous hydrogen peroxide solution further comprises the step of washing the semiconductor substrate with deionized water. The method of forming a metal ruthenium as described in claim n, wherein the immersing the semiconductor substrate in an aqueous hydrogen peroxide solution further comprises the step of washing the semiconductor substrate with deionized water. 2 〇 a method for forming a metal halide, comprising the steps of: providing a germanium substrate having a polysilicon gate formed thereon, wherein the polysilicon gate has a spacer, wherein the poly gate is formed of a polycrystalline germanium; Forming a metal layer and a barrier layer in sequence on the surface of the substrate and the gate of the polysilicon gate; The ruthenium substrate is tempered to form a residual metal lithium compound by the 夕 ^ ^ t Λ 该 该 基 基 基 基 基 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The substrate is immersed in an aqueous solution of hydrogen peroxide in an amount of 14 L to form an n + C ^ ^ „ shape A/month wash to remove the oxidized dystrophic gland layer and the unreacted metal layer, wherein the prepared 丄τ 又 、 、 、 、 、 1299530 Case No. 91112080 q 曰 Amendment 6. Patent application scope and immersion of the ruthenium substrate in a mixed solution of phosphoric acid, nitric acid and acetic acid to remove the reaction product of the residual non-metal ruthenium compound. The method of forming a metal halide according to the second aspect of the invention, wherein the ruthenium substrate is immersed in an aqueous hydrogen peroxide solution and further comprises the step of washing the stone substrate with deionized water. The method of forming a metal halide according to the second aspect of the invention, wherein the ruthenium substrate is immersed in an aqueous hydrogen peroxide solution and further comprises the step of washing the ruthenium substrate with deionized water. The method of forming a metal telluride as described in claim 2, wherein the spacer is tantalum nitride. The method of forming a metal telluride as described in claim 2, wherein the metal layer is a cobalt metal layer. 2 5 The method for forming a metal halide according to the second aspect of the patent application, wherein the barrier layer is one of a titanium-containing metal layer or a nitrided titanium-containing metal layer. The method of forming a metal halide according to the item, wherein the metal halide is cobalt telluride. The method of forming a metal halide according to the second aspect of the invention, wherein the reaction product of the residual non-metal halide is cobalt oxide or trioxide. 28. The method of forming a metal halide according to the second aspect of the patent application, wherein the composition ratio of the mixed solution is phosphoric acid: nitric acid: acetic acid = 70 ·· 10 : 2-3 〇 〇503-7727T»Fl(NT);TSMC2〇〇M569.ptc Page 17 Case No. 911〗 2080 1299530 VI. Patent application scope 29. A method for forming a metal telluride, comprising the following steps: providing a stone-base substrate, wherein a polycrystalline stone is formed on the base of the stone, and a sidewall of the polycrystalline gate is formed. Having a spacer; forming a cobalt metal layer and a titanium-containing metal layer in sequence on the stone substrate and the polycrystalline silicon gate electrode; tempering the germanium substrate to make the germanium substrate And forming a cobalt bismuth layer on the surface of the polysilicon gate, wherein an oxidation initiation layer is formed on the surface of the spacer; the ruthenium substrate is immersed in an aqueous solution of hydrogen peroxide to remove the titanium-containing metal a layer and an unreacted cobalt metal layer, wherein the aqueous hydrogen peroxide solution does not include ammonia water; and the ruthenium substrate is immersed in a mixed solution of phosphoric acid: nitric acid: acetic acid: 7 〇: 1 〇: 2-3 to remove the cobalt oxide layer . The method of forming a metalloid compound according to claim 29, wherein the ruthenium substrate is immersed in an aqueous hydrogen peroxide solution and further comprises the step of washing the ruthenium substrate with deionized water. The method of forming a metal halide according to claim 29, wherein the ruthenium substrate is immersed in an aqueous hydrogen peroxide solution and further comprises the step of washing the stone substrate with deionized water. 32. The method of forming a metal halide according to claim 29, wherein the spacer is tantalum nitride. 0503-7727TWFl(N);TSMC2001-1569.ptc Page 18