TW554382B - Method of forming TiSiN film, diffusion preventing film and semiconductor device constituted by TiSiN film and method of producing the same, and TiSiN film forming device - Google Patents

Abstract

This invention utilizes a TiSiN film as barrier metal in a semiconductor device so as to prevent diffusion of copper. The TiSiN film is formed by plasma CVD or hot CVD. When the film is formed by hot CVD, TiCl4, gases of silane, and NH3 gas are used as raw material gases. When the film is formed by plasma CVD, TiCl4, gases of silane, H2 gas, and N2 gas are used as raw material gases.

Description

554382 A7 B7 V. Description of the invention (1) The present invention relates to a barrier layer used in a semiconductor device and a method for manufacturing the same, and a semiconductor device using the barrier layer and a manufacturing method thereof (please read the precautions on the back first) Fill out this page again). Generally, when manufacturing a semiconductor integrated circuit, substrates such as semiconductor wafers are repeatedly subjected to film formation and 囷 -etching to form a large number of predetermined elements. However, the wiring that can be connected between various elements is to prevent the substrate from being used as the base and the film layer containing Si from interfering with the wiring material due to the absorption of silicon. Generally, a barrier metal is also interposed between the base and the substrate. Those who can be used as the barrier metal are, of course, those having low resistance, and materials having excellent corrosion resistance must be used. At present, most of the wiring materials used are aluminum wiring and tungsten wiring. The materials that use the barrier metal that can meet the aforementioned requirements are nitrides of high melting point metal materials such as Ti (titanium), W (tungsten), and Mo (molybdenum). Among the above metal materials, Ti has good electrical and corrosion resistance characteristics, so it is particularly preferred to use a Ti film or a TiN film. The Ti film and TiN film printed by the Industrial and Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs as barrier metals are generally formed in the South temperature area around 500 ~ 700 ° C and formed by CVD (Chemical Vapor Deposition). For large aspect ratio contact The channels and transfer channels can also be effectively buried, and the characteristics of aluminum and tungsten for wiring materials are also good. However, according to the recent demand for high integration and miniaturization of integrated circuits, it is practical to make the line width narrower than that of wiring and so on, and to require a line width smaller than or equal to 0.2 μm. In addition, at the same time as increasing the integration, the high-speed operability of the integration circuit is also strongly required. Under such demand, copper, which can replace IS as a wiring material, is cheaper and has a smaller resistivity. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 554382-· Ministry of Economics and Intellectual Property Bureau X Fei Heshe printed% A7 B7 5. Description of the invention (2 attracted much attention. However, as is well known, copper and aluminum are also likely to cause migration to Shi Xi, as well as to copper, and then diffuse at low temperatures. The barrier metal of the Ti film and TiN film used makes the barrier property insufficient. Once the material is used, in order to fully ensure the barrier property, the film thickness must be thickened to a certain degree. It is not appropriate for components whose body height is also restricted in the cross-section height direction. Because the wiring portion must be formed within a predetermined cross-sectional area, the cross-sectional area of the barrier metal layer portion is increased, which is relatively constant. It is necessary to reduce the load area occupied by the wiring material and increase the wiring resistance. As a result, when copper is used as the wiring material, the effective barrier metal layer is now There is a strong need for development. The present invention is directed to the above problems and was created by the present invention in order to effectively solve the above problems. A first object of the present invention is to provide a copper wire material that effectively prevents the diffusion of metals and the like. The second object of the present invention is to provide a semiconductor device using the diffusion preventing film and a method for manufacturing the same. The third object of the present invention is to provide a method for manufacturing the diffusion preventing film. To achieve the above object, the present invention The invention provides a method for manufacturing a TiSiN film, which is characterized by including the following steps: ... for supplying a film-forming gas containing a Ti-containing gas, a Si-containing gas, and an N-containing gas to a reaction chamber; and The aforementioned film-forming gas is in contact with a heated substrate placed in a room, and a film containing TiSiN is formed on the aforementioned substrate by thermal CVD. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

554382 A7 B7_ V. Description of the invention (3) (Please read the precautions on the back before filling this page) The aforementioned Ti-containing gas system should be used for TiCl4, tetrahydroxydimethylamino titanium and tetrahydroxydiethylamino titanium. At least one of them. In addition, the aforementioned gas-containing gas is preferably at least one of SiH2Cl2, SiHCl3, SiCl4, Si2H4, and Si2H6. Furthermore, the aforementioned N-containing gas is preferably used as at least one of NH3 and monomethylhydrazine. In addition, the present invention provides a method for manufacturing a TiSiN film, which is characterized by including the following steps: one for supplying Si-containing gas, TiCU gas radon, n2 gas, and reducing gas into the processing chamber; A person who generates a first plasma with a gas, a TiCU gas, a gas, and a reducing gas; and a person who forms a film containing TiSiN on a substrate by using the aforementioned first plasma; and a gas for supplying krypton and N into the reaction chamber A second plasma generated by the aforementioned gas containing ytterbium and nitrogen; and a surface treated by the second plasma with the TiSiN-containing film to remove α from the aforementioned film. The aforementioned Si-containing gas system is preferably at least one of SiH2Cl2, SiHCl3, SiCl4, Si2H4, and Si2H6. In addition, the aforementioned reducing gas system can be used as H2 or nh3 gas. In particular, the Si-containing gas system uses SiH4 gas, and the reducing gas is preferably H2 gas. The Intellectual Property Bureau of the Ministry of Economic Affairs 2 (Industrial and consumer cooperatives printed in the aforementioned step for generating the first plasma, the substrate should be heated to 350 ~ 450t :. Also, in the foregoing for generating the first plasma In the step, the pressure in the aforementioned reaction chamber should be 0.5 ~ 5 but ΓΓΓ. In addition, in the step for supplying Sih-containing gas, Tici4 gas, N2 gas, and reducing gas into the reaction chamber, it should be The SiH4 gas is 0.1 to 10 sccm, the TiCl4 gas is 1 to 10 sccm, the n2 gas is 30 to 500 sccm, the h2 gas is 100 to 300 sccm, and the metallurgical gas is 100 to 200. 〇sccm. This paper size applies the Chinese National Standard (CNS) A4 specification (2 · 10 × 297 mm) 6 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Industrial Cooperatives ^ 554382 A7 B7 V. Description of the invention (4) The aforementioned method is acceptable After the step of forming a film containing TiSiN on a substrate, the method further includes a step of removing the aforementioned reaction chamber or the components in the aforementioned chamber by using a gas containing C1F3. In addition, the present invention provides a film made of TiSiN Constitutive expansion prevention film, the The film is formed by plasma CVD or thermal CVD. When forming a film containing TiSiN by plasma CVD, the composition of the film includes 10 to 40 at% Ti, 10 to 40 at 0 / 〇 Si, and 25 to 47 at% of N is preferred. In addition, the aforementioned TiSiN-containing film system contains 28 to 32 at% of rhenium, 20 to 25 at% of Si, and 28 to 32 at% of N. It is more preferred. The composition ratio film is preferably formed by high-pressure operation (such as an operating pressure of 3 Torr). In addition, the aforementioned TiSiN-containing film system contains 24 to 36 at% Ti, 11 to 22 at% Si, and 44 to 46 at%. The N is better. Also, the film with this composition ratio is preferably formed by low-pressure operation (such as operating pressure of 0.6 ΤΟ1Γ). The aforementioned TiSiN-containing film is disposed between the Si layer and the Cu layer. It is used as a good barrier metal. In addition, the present invention provides a semiconductor device, which is characterized by having a capacitor portion, which includes an insulating layer composed of a material having a high dielectric constant. ; The lower electrode layer, which is provided below the aforementioned insulating layer; the upper electrode layer, which is provided on the aforementioned insulating layer In addition, it is composed of a film containing TiSiN formed by plasma CVD or thermal CVD: and a barrier layer, which is provided between the aforementioned insulating layer and the lower electrode layer. Furthermore, the present invention provides a semiconductor device. It is characterized by a capacitor section, which includes: an insulation layer, which conforms to the Chinese National Standard (CNS) A4 specification (210X297 mm) — I-packed I-line (please read the precautions on the back first) (Fill in this page again) 554382 Printed by Xiao Gong Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs

A7 B7 V. Description of the invention (5) Made of materials with high dielectric constant; lower electrode layer, which is provided below the aforementioned insulating layer; upper electrode layer, which is provided above the aforementioned insulating layer; The barrier layer is formed between the aforementioned insulating layer and the lower electrode layer, and is also composed of a film containing TiSiN formed by plasma CVD or thermal CVD. Furthermore, the present invention provides a semiconductor device, which is characterized by having a capacitor portion. The capacitor portion includes: an insulating layer composed of a material having a high dielectric constant; and a lower electrode layer, which is The upper electrode layer is provided below the aforementioned insulating layer; the barrier layer is provided below the aforementioned lower electrode layer, and is simultaneously formed by plasma CVD or thermal CVD It is composed of a film containing TiSiN; and a wiring layer, which is provided under the aforementioned barrier layer. At least one of the upper electrode layer and the lower electrode layer may be composed of Pt or Ru. The upper electrode layer may be a TiSiN film formed by plasma CVD or thermal CVD. In addition, a semiconductor device can be constructed in which a barrier layer made of a film containing TiSiN formed by plasma CVD or thermal CVD is further provided on the upper electrode layer. In addition, the present invention provides a semiconductor device, which is characterized by having a capacitor portion including: an insulating layer made of a material having a high dielectric constant; and a lower electrode layer made of The upper electrode layer is composed of the TiSiN film provided under the aforementioned insulating layer; the upper electrode layer is provided above the aforementioned insulating layer, and is prepared by plasma CVD or thermal CVD (please read the precautions on the back before filling in this page)

、 1T This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 554382 A7 B7 V. Description of the invention (6) Formed by a film containing TiSiN; barrier layer, which is provided on the aforementioned lower electrode A layer underneath the layer; and a wiring layer which is provided under the aforementioned barrier layer. The aforementioned material with a high dielectric constant may be formed of a material selected from the group consisting of (Ba, Sr) Ti03, Pb (Zr, Ti) 03, Ta205, and RuO. The present invention also provides a semiconductor device including: a wiring layer; a buried wiring portion connected to the aforementioned wiring layer and a diffusion layer formed on a semiconductor substrate or an upper portion; and a barrier layer, It is formed between the above-mentioned buried wiring portion and a diffusion layer formed on a semiconductor substrate or an upper part thereof, and at the same time is composed of a film containing TiSiN formed by plasma CVD or thermal CVD. Furthermore, the present invention provides a semiconductor device, comprising: a semiconductor substrate; and a gate electrode formed on the main surface of the semiconductor substrate with an insulating layer as an intermediary, and connecting the wiring layer at the same time: The gate electrode is composed of a TiSiN-containing film formed by plasma CVD or thermal CVD. The structure of the foregoing gate electrode may include: a lower layer composed of a film containing TiSiN formed by plasma CVD or thermal CVD; and an upper layer formed by W formed on the foregoing lower layer. The gate electrode system includes an insulating layer formed on the semiconductor substrate, and at the same time, one selected from the group consisting of (Ba, Sr) Ti03, Pb (Zr, Ti) 03, Ta205, and RuO. Material composition; barrier layer, which is composed of the TiSiN film formed on the aforementioned insulation layer; the dimensional dimensions are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -------- -Installation ------ Order the line (please read the precautions on the back before filling this page) 9 554382 A7 B7 V. Description of the invention (Electric layer, which is formed above the aforementioned barrier layer. (Please read first Note on the back side, please fill in this page again.) Furthermore, a film layer made of SiOxNy film can be further provided between the aforementioned semiconductor substrate and the aforementioned insulating layer. In addition, the present invention provides a method for manufacturing a semiconductor device. It is characterized by including a step for forming a capacitor portion, which includes the following procedures: forming a lower electrode layer; and forming a film containing TiSiN formed by plasma CVD or thermal CVD on the lower electrode layer. Barriers Those used to form an insulating layer made of a material with a high dielectric constant on the aforementioned barrier layer; and those used to form an upper electrode layer on the insulating layer. Furthermore, the present invention provides a method for manufacturing a semiconductor device, which The method is characterized in that it includes a step for forming a capacitor portion, which includes the following procedures: forming a lower electrode layer; forming a barrier layer on the aforementioned lower electrode layer; forming on the aforementioned barrier layer Those who have an insulating layer made of a material with a high dielectric constant; and those who use it to form an upper electrode layer made of a film containing TiSiN formed by plasma CVD or thermal CVD on the insulating layer. Intellectual Property of the Ministry of Economic Affairs Bureau g (printed by Industrial and Consumer Cooperatives) and the present invention provides a method for manufacturing a semiconductor device. The method is characterized in that it includes a step for forming a capacitor portion. The step includes the following procedures: A barrier layer is formed on the wiring layer on the substrate, and the barrier layer is formed by a film containing TiSiN formed by plasma CVD or thermal CVD. · For the barrier layer in the lower electrode layer are formed thereon; forming an insulating layer configured by having a high dielectric constant of the material constituting the upper layer to the lower electrode; and configured on the insulation layer

10 · 554382 0 A7 B7 V. Description of the invention (8) The upper electrode layer is formed on the surface. The present invention also provides a method for manufacturing a semiconductor device, which is characterized by including a step for forming a capacitor portion. The step includes the following procedure: forming a layer of TiSiN on a wiring layer formed on a semiconductor substrate; A barrier layer made of a film; a layer for forming a lower electrode layer on the foregoing barrier layer; a layer for forming an insulating layer made of a material with a high dielectric constant on the aforementioned lower electrode layer; and a layer for insulating On the layer, an upper electrode layer composed of a TiSiN-containing film formed by plasma CVD or thermal CVD is formed. The invention also provides a method for manufacturing a semiconductor device, which is characterized by including a step for forming a capacitor portion. The step includes the following procedures: forming a lower portion on a wiring layer formed on a semiconductor substrate Electrode layer 'The lower electrode layer is formed by a film containing TiSiN formed by plasma CVD or thermal CVD; used to form an insulating layer made of a material with a high dielectric constant on the aforementioned lower electrode layer; and Those used to form an upper electrode layer on the insulating layer. The upper electrode layer is formed by a film containing TiSiN formed by plasma CVD or thermal CVD. In addition, the present invention provides a method for manufacturing a semiconductor device. The method is characterized by including a step for forming a buried wiring portion, which includes the following procedures: a semiconductor substrate or a conductive layer on the substrate Those who form an insulating layer thereon; those who form a contact channel or a transition channel by etching on the aforementioned insulating layer; those who form a barrier layer made of a TiSiN film on the aforementioned insulating layer and in the aforementioned contact channel or via channel; and Those used to form a wiring layer on the barrier layer. This paper size is applicable to Chinese National Standard (CNS) Ya 4 threats (210X297 mm) --------- g ------ IT ------ line (please read the note on the back) Please fill in this page again) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperative, 11 554382 A7 B7 V. Description of Invention (9) " " ^ (Please read the precautions on the back before filling this page) The invention provides a method for manufacturing a semiconductor device. The method is characterized in that it includes a step for forming a gate electrode. The step is provided with the following procedure: it is used to form a plasma CVD on a semiconductor substrate with an insulating layer as an intermediary. Or a thermal CVD film containing a TiSiN layer; and a layer for forming an upper layer made of W on the lower layer. The invention also provides a method for manufacturing a semiconductor device. The method is characterized by including a step for forming a gate electrode. The step is provided with the following procedure: for forming a material with a high dielectric constant on a semiconductor substrate. Those composed of an insulating layer; those used to form a barrier layer composed of a film containing TiSiN by plasma CVD or thermal CVD on the insulating layer; and those used to form a conductive layer on the aforementioned barrier layer. At this time, the aforementioned step for forming a gate electrode further includes a procedure for forming a SiOxNy film between the semiconductor substrate and the insulating layer. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the present invention provides a film-forming device, which is characterized by comprising: a reaction chamber for receiving substrates to be processed; and a support member for supporting indoors A substrate to be processed; a film-forming gas introduction mechanism for introducing a film-forming gas into a reaction chamber; and a heating mechanism for heating a substrate to be processed supported by the support member; and the film-forming gas introduction The mechanism has a supply source of Ti-containing gas, Si-containing gas, and N-containing gas, and the TiSiN-containing film is formed by thermal CVD on a substrate to be processed heated by the aforementioned heating mechanism. The foregoing and other features of the present invention will be made clear by reference to the following description. This paper size applies Chinese national standard (CNS> A4 specification (210X297 mm) 12 Printed by the Industrial and Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 554382 A7 B7 V. Description of the invention (10) Brief description of the drawing A schematic cross-sectional view of a thermal CVD device during film formation of a TiSiN film. Figure 2 is a schematic diagram illustrating a method for evaluating step coverage. Figure 3 shows an example of the method according to the present invention The obtained TiSiN film is used for the cross section circle of a capacitor structure for DRAM and the like. FIG. 4 shows an example of the cross section 圊 of the capacitor structure for the TiSiN film obtained by the method of the present invention. FIG. 5 Another example is shown in which the TiSiN film obtained by the method of the present invention is used for the cross section 囷 of a capacitor structure for a DRAM, etc. Fig. 6 shows another example where the TiSiN film obtained by the method of the present invention is used in The cross-section circle of the capacitor structure of DRAM, etc. Fig. 7 shows another example, the cross-section 圊 of the capacitor structure of DRAM, etc., using the TiSiN film obtained by the method of the present invention. Fig. 8 shows For example, the TiSiN film obtained by the method of the present invention is used as a carrier surface of a capacitor structure of a DRAM, etc. Fig. 9 shows yet another example, the TiSiN film obtained by the method of the present invention is used for DRAM, etc. The load-bearing surface of the capacitor structure is round. Figure 10 shows an example of the cross section 接触 of the contact portion of the metal wiring layer using the TiSiN film obtained by the method of the present invention. Figure 11 shows an example of the method according to the present invention The TiSiN film obtained by the method is used for wearing on the gate electrode. Figure 12 shows another example. The paper size obtained according to the method of the present invention applies the Chinese National Standard (CNS) A4 specification (210X297 mm). ) III n IIIIIIIIIII order — III ~~ ~ line (please read the note on the back before filling this page) 13 554382 A7 B7 V. Description of the invention (1) Figure 27 shows the flow of SiH4 gas during low pressure operation and The obtained relationship diagram of the barrier properties of the TiSiN film. (Please read the precautions on the back before filling this page) The best mode for implementing the present invention The following describes the details of the present invention with reference to the attached drawings. In addition, there are two types of film forming methods of the present invention. Those who perform thermal CVD and those who perform plasma CVD will first explain the method of performing thermal cvd. TiSiN by thermal CVD The first film formation is a cross-sectional view of a thermal CVD device for forming a film containing TiSiN by thermal CVD on a wafer. In the following description, the substrate to be processed is directed to a semiconductor wafer. The presenter is not limited to such a substrate, and other types of substrates may be used. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the thermal CVD device 10 has a gas-tight and slightly cylindrical reaction chamber 11, and a cylindrical-shaped support member 13 is arranged in the reaction chamber 11 to remotely and The susceptor 12 capable of horizontally supporting the semiconductor wafer W of an object to be processed. A guide ring 14 for guiding the semiconductor wafer w is provided on the outer edge portion of the base 12. Further, a heater 15 is buried in the susceptor 12, and the heater 15 is heated by a power source 16 to heat the semiconductor wafer w of the processing object to a predetermined temperature. A controller 17 is connected to the power supply 16 to control the output of the heater 15 in response to a signal from a temperature sensor (not shown). A shower head 20 is provided on the top wall 11a of the reaction chamber 11, and the constitution is such that a gas for film formation is introduced from the shower head 20 toward the reaction chamber 11. The film-forming gas system uses Ti-containing gas, Si-containing gas, and N-containing gas. Ti-containing gas systems such as TiCl4, tetrahydroxydimethylamino titanium (TDMAT) The paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 public love) 15 554382 A7 B7 V. Description of the invention (13), And tetrahydroxydiethylaminotitanium (TDEAT), Si-containing systems are used for

SiH2C12, SiHC13, SiCl4, Si2H4, Si2H6, and n-containing gas use --------------- II (Please read the precautions on the back before filling out this page) For example, NH3 and single Methylhydrazine (MMH). The first example shows that the gas containing T1 is T1CI4, the gas containing Si is SiHjCl2, and the gas containing N. It is NH3, and the following description is given for the state of using these gases. At the shower head 20, a plurality of gas discharge holes 20a and 20b are formed alternately to the base 12 for gas discharge. Then, the shower head 20 is connected to the piping of the gas supply mechanism 30. As described later, the gas discharge hole 20a is connected to the piping 45 for supplying TiCU gas, and the gas discharge hole 20b is used to supply NH; The gas piping 46 is connected, and its structure is for introducing a predetermined gas into the reaction chamber 11 through the shower head 20. In this way, the shower head 20 is a matrix type, and the discharge method is TiCU gas, SiH2Cl2 gas, and NH3 gas that are used to discharge reaction gas from different and interactively formed discharge holes. Post-mixing is performed after mixing. 〇 Intellectual Property Bureau of the Ministry of Economic Affairs : A (Industrial and consumer cooperative printed gas supply mechanism 30 is provided with a CIF3 supply source 31 for supplying ciF3 for removing gas, a supply of > 1 of 12 < 12 supply source 32, and a supply of butan iCl4 for supplying TiCl4. Source 33, SiH2Cl2iSiH2Cl2 supply source 34, NH3 supply source 35 for supplying NA gas, and then each of the above supply sources is connected with a passage, that is, C1F3 supply source 31 is connected to air pipe 39, and supply source 32 It is connected to gas pipe 40, TiCl4 supply source 33 and gas pipe 41, SiH2Cl2 supply source 34 and gas pipe 42, and NH3 supply source 35 and gas pipe 43. Then, each gas pipe is provided with a valve 47 and a mass flow controller 48. Supply by A The gas pipe 40 extended by the source 32 merges with the gas pipe 41 extended by the TiCl4 supply source 33. The TiCl4 gas carried by the N2 gas passes through the gas pipe 40. The paper size applies the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm). 16 554382 Intellectual Property Bureau of the Ministry of Economic Affairs: Printing A7 B7 by the Industrial and Commercial Cooperatives 5. Description of the invention (14) and piping 45 to reach the shower head 20, which is introduced into the reaction chamber 11 from the gas outlet hole 20a. It is supplied from C1F3 31. The extended gas pipe 39 merges with the gas pipe 40. By opening the valve provided on the gas pipe 39, the cleaned gas C1F3 passes through the gas pipes 39, 40 and the piping 45 to reach the shower head 20, and the gas discharge hole 20a is directed to the reaction chamber 11 In addition, the NH3 system is introduced from the NH3 supply source 35 through the air pipe 43 and the piping 46 to the shower head 20, and is introduced into the reaction chamber 11 through the gas discharge hole 20b. The gas pipe 42 and the air pipe extended by the SiH / b supply source 34 41 is connected, through SiHfl2 air pipe 42, air pipe 41, air pipe 40 and piping 45, reaches the shower head 20, and is introduced into the reaction chamber 11 through the gas outlet hole 20a. The TiCl4 supply source 33 and the TiCl4 supply source 33 up to the reaction chamber 11 The gas pipe and the mass flow controller 48 are heated by a heating device (not shown) so that TiCl4 does not condense. Furthermore, the top plate and the peripheral wall of the reaction chamber 11 are also heated. In addition, the aforementioned carrier gas may be replaced by Ar or the like instead of N2 。 Reaction chamber An exhaust pipe 18 is connected to the wall lib, and the exhaust pipe 18 is connected to an exhaust device 19 provided with a vacuum pump. When the exhaust device 19 is operated, the reaction chamber 11 can be decompressed to a predetermined vacuum. Next, an example of a method for forming a TiSiN film on the semiconductor wafer W by the above apparatus will be described. First, the semiconductor wafer W is loaded into the reaction chamber 11, while the wafer w is heated by the heater 15, and the inside of the reaction chamber 11 is exhausted by the exhaust device 19, so that the reaction chamber 11 is in a vacuum state, and then the The flow ratio is to introduce the N2 gas and the NH3 gas into the reaction chamber η, so that the reaction chamber η displays, for example, 133.3 to 1333.2 Pa (1 to 10 Torr), and then preliminary calcination is performed. Secondly, the pressure intended for film formation is formed in the reaction chamber 11, and the paper size is adapted to the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- ^ ----- -1T ------ i (Please read the precautions on the back before filling out this page) 17 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Industrial and Consumer Cooperatives 554382 A7 B7 V. Description of the invention (15) Helium gas and NH3 gas The flow rate is constant, so that TiCl4 gas and SiH2Cl2 are flowed in at a certain flow ratio in the period of 5 to 20 seconds, and then the TiSiN film is processed in the same conditions as in the previous flow and the film is processed in a predetermined time. . The best examples of film formation conditions at this time are as follows. Working pressure: 40 · 0 ~ 666.6Pa (0.3 ~ 5Torr)

Wafer temperature: 400 ~ 650 ° C

TiCU gas flow rate 3.0xl0-4 to 3.0xl (K3ni3 / sec (5 to 50sccm) NH3 gas flow rate 3.00x 10 · 3 to 3 · 0x 10-2m3 / sec (50 to 500sccm) gas flow rate: 3.0x10 -4 ~ 3.Ox 1 (T2ni3 / sec (5 ~ 500sccm) In this way, the TiSiN film is formed on the uneven portion by thermal CVD, and good step recovery (effect) can be obtained. That is, the formation by thermal CVD When it is a film, it is different from the case of plasma CVD. It has a surface reaction and can basically increase the step recovery. Therefore, it can form a thin film thickness and improve the miniaturization of the device. As shown in the figure, when the channel portion η is provided, the thickness of the film formed outside the channel portion Η is a, and the thickness of the film formed at the bottom of the channel portion is B ', and the thickness of the film formed at the side portion of the channel portion is c, It can be used to evaluate B / A at the bottom and C / A at the side. Specifically, as shown in Figure 2, the channel part with a gap of about 0.2 μm and a depth of about 0.5 μm is borrowed according to the method described above. cvd to form the standard of this paper applies the Zhongguanjia Standard (CNS) Α4 specification (210X297 mm) '~--* --------- 0-- (Please read the back first Notes on filling out this page) booked 18 554382 A7 B7 economy - Ministry wisdom property bureau of consumer cooperatives PRINTED V. Description (16 invention

For TiSiN film, the bottom recovery and side recovery are both above 90%. In contrast to this result, when plasma deposition is generally performed by plasma CVD, the above values are within 20 to 30%. It is also known that, according to the foregoing method, when a TiSiN film is formed by thermal CVD, although the film formation temperature is higher than that of a conventional plasma CVD film formation, good film quality can still be formed. In this way, after the TiSiN film is formed, the semiconductor wafer is taken out from the reaction chamber 11, and then the AN2 gas (ar gas may be used) and the C1F3 gas for removing the gas are conducted into the reaction chamber 11 to remove the inside of the reaction chamber 11. In addition, the removal conditions are preferably the following. Temperature: 200 ~ 500 ° C (more preferably 200 ° C) Film formation pressure: 0.5 ~ 5Torr (more preferably 3Torr) C1F3 gas flow rate: 100 ~ 500sccm (more preferably 200sccm) N2 gas ( The same is true when using Ar gas): 100 ~ 500sccm (more preferably 200sccm). So the TiSiN film can be easily cleaned by using C1F3 gas removal gas. Each time a film-forming process is performed on an appropriate number of wafers, cleaning the reaction chamber with C1F3 gas can suppress the generation of dust particles and enable high-quality film formation. The removal of the C1F3 gas is effective even for a TiSiN film formed by a plasma treatment described later. Next, a usage example of the TiSiN film will be described. In the following use cases, the TiSiN film can be formed by the aforementioned method. A method for forming a layer other than the T ^ iSiN film may be a known method unless otherwise specified. FIG. 3 is a diagram showing a round surface of an embodiment in which a TiSiN film is used for a MIS (Metal Isoration Silicon) type capacitor structure of a DRAM or the like. The basic paper size of Si is applicable to China National Standard (CNS) Α4 specification (210X29 * 7mm) --------- install ------, π ------ 0 (Please read the back first Please note this page, please fill out this page) 19 554382 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (17) Impurity diffusion field 50a of plate 50 is followed by lower electrode layer 51 composed of amorphous Si, And on the lower electrode layer 51, a SiN resist layer 52 formed by applying #rtn (Rapid Thermal Nitrization) on silicon is used as an intermediary, and formed by BST, Pb (Zr, Ti) 03 (PZT), Ta205 or An insulating layer 53 made of a high-permittivity material is further formed with an upper electrode layer 54 formed of a TiSiN film thereon. A metal wiring layer (not shown) is then formed on the upper electrode layer 54. In addition, it is known to use a TiN film as the upper electrode layer 54, but it has such a problem that 0 of Ta205 will be diffused in the TiN film by a subsequent step of heat treatment and converted into TiO, resulting in a reduction in the film thickness of the TiN film. , Which causes the film thickness of Ta205 to become thicker and the capacity to be reduced. This problem can be solved by using the upper electrode layer 54 formed of a TiSiN film. Fig. 4 shows the same basic structure as the third circle, except that the SiN barrier layer 52 on the lower electrode layer 51 is replaced with a barrier layer 55 made of a TiSiN film. Thereby, the barrier properties between the lower electrode layer 51 and the insulating layer 53 can be further improved. Fig. 5 is a cross-sectional view showing an embodiment of a structure of a MIM (Metal Isortion Metal) capacitor of a TiSiN film formed by thermal CVD according to the present invention for use in a DRAM or the like. A barrier layer 62 made of a TiSiN film is formed on the poly Si plug (wiring layer) 61 that is continuous with the impurity diffusion region of the Si substrate. A lower electrode 63 made of Pt, Ru, etc., an insulating layer 64 made of a high permittivity material of BST, Pb (Zr, Ti) 03 (PZT), Ta205, or RuO are sequentially formed on the barrier layer 62, and Upper electrode layer 65 composed of Pt, Ru, etc. (Please read the precautions on the back before filling this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) 20

I Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Industrial and Consumer Cooperatives 554382 A7 B7 V. Description of the Invention (18) " " According to the above structure, the aforementioned high permittivity material is used as the insulating layer 64 'capacitor that can be used as part of DRAM memory To obtain a large capacity and reduce the density of leakage current. In addition, pt, Ru & used in the electrode material can reduce the density of leakage current, so it can be combined with high density and high integration of semiconductor devices. In addition, Pt and RU are used instead of Si for the electrodes, so that high speed can be achieved. Furthermore, by forming the barrier layer 62, the lower electrode 63 can be effectively prevented from reacting with the polysilicon plug 61 under the electrode, and when the insulating layer 64 is formed, the diffusion of oxygen can be prevented to prevent the oxidation of the polysilicon plug 61. This can prevent the increase in resistance. Figure 6 is used to show the structure of MIM capacitors. The difference is that in Figure 5 the upper electrode 65 made of Pt, Ru, etc. is replaced by the upper electrode 66 made of TiSiN film; the 7th series In order to show that in addition to forming the upper electrode 66 as described above, the lower electrode 63 made of Pt, Ru, etc. in the fifth step is replaced by a lower electrode 67 made of a TiSiN film. In particular, as shown in Fig. 7, since the lower electrode is formed by a TiSiN film having good barrier properties, the barrier device 62 is not required, and the semiconductor device can be miniaturized. Also, in the structure of the fifth circle, as shown in FIG. 8, the reaction between the upper electrode 65 and a wiring layer (not shown) on the electrode can be reliably prevented. A blocking layer 68 made of a Ding film is formed on 65.

Fig. 9 is a view showing a wearing surface of the TiSiN film when it is used at a contact portion of a metal wiring layer. An interlayer insulating film 71 is formed on the Si substrate 70. A contact channel 72 is formed in the interlayer insulating film 71 so as to reach the impurity diffusion region 70a of the Si substrate 70. The interlayer insulating film 71 and the contact channel 72 are formed on the TiSiN paper standard (CNS) subordinate grade (21GX 297) while quoting a-• 21-^-(Please read first (Notes on the back then fill out this page)

* 1T 554382 A7 B7 V. Description of the invention (19) (Please read the precautions on the back before filling this page) The barrier layer 73 made of film. On the barrier layer 73, a metal wiring layer 74 made of W is formed. The metal wiring layer 74 composed of this layer w is also filled in the contact channel 72 to form a buried wiring portion 74a, thereby bringing the impurity diffusion region 70a of the Si substrate 70 into communication with the metal wiring layer 74. Since the barrier property of the TiSiiSi film is much higher than that of the conventional TiN film, it is very effective to prevent the W of the metal wiring layer 74 having the film from reacting with the Si phase at the base to form a compound. As the barrier layer, another wiring layer formed of Cu & Ai or the like can be used as the TiSiN film system. FIG. 10 shows the morphology of a TiSiN film when used as a gate electrode. A lower layer 82 composed of a TiSiN film formed by thermal CVD is provided on the Si substrate 80 with an insulating film 81 as an intermediary, and a gate electrode 84 composed of an upper layer 83 formed of a W thin film on the layer is formed on the upper layer 83. There is a W wiring layer 86. The symbol 85 in 囷 refers to a spacer made of SiN. The TiSiN film used as the gate electrode is low-resistance, has excellent barrier properties, and is thermally stable. It also shows excellent characteristics when used as a gate electrode. Figure 11 printed by the Industrial and Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs shows that an insulating layer made of a high dielectric material of BST, Pb (Zr, Ti) 03 (PZT), Ta205, or RuO is formed on the Si substrate 80. 86 'and a barrier layer 87 made of a TiSiN film is formed thereon, and an upper layer 88 made of an Al or W film is formed thereon to form a gate electrode 89. 90 and 91 in FIG. 11 indicate a source and a drain. In the twelfth series, a SiOxNy thin film 92 is formed on the Si substrate 80, and an insulating layer made of a high-dielectric material such as BST, Pb (Zr, Ti) 03 (PZT), Ta205, or RuO is formed thereon. 93, and a barrier layer 94 made of TiSiN film is formed thereon, and an upper layer made of A1 or W film is formed thereon. The paper size is applicable to China National Standard (CNS) A4 (210x297 mm) 22 554382 A7 B7 Economy-Ministry of Wisdom. ¾ The Bureau of Property «Printed by the Agency 五. V. Invention Description (20) 95 to form the gate electrode 96. The above structures can respond to high speed. The barrier layers 87 and 94 made of TiSiN film can effectively prevent the mutual diffusion between the upper layers 88 and 95 and the insulating layers 86 and 93 made of a high dielectric material. In addition, in Fig. 11, when the insulating layer 93 is directly contacted on the Si substrate 80, an interface defect occurs, and it is difficult to apply interface control. At this time, as shown in Fig. 12 (a), after 8? 02 is formed between the Si substrate 80 and the insulating layer 93, a nitrided SiOxNy film 92 is provided on the surface to solve the foregoing problem. In addition, the TiSiN film can be formed by the thermal CVD and the plasma CVD described later, and can also exhibit excellent barrier properties when formed by any method. In addition, when thermal CVD or plasma CVD is used, an excellent step recovery effect can be obtained compared with a method of forming a film by conventional PVD. Therefore, miniaturization of a semiconductor device can be easily performed. In addition, when the film is formed by thermal CVD, an extremely excellent step recovery effect can be obtained. On the other hand, when the TiSiN film is formed by plasma CVD, the step recovery effect is lower than that of plasma CVD which is used for thermal CVD. It can also be processed at a lower temperature than thermal CVD. Therefore, it has an advantage that Cu is present at the base In the layer, the diffusion of Cu to the TiSiN film can be suppressed to a minimum. Film Formation of TiSiN Film by Plasma CVD Next, film formation of a TiSiN film by plasma CVD will be described. Fig. 13 is a schematic view showing a configuration of a plasma film forming apparatus used for forming a TiSiN film. The plasma film-forming apparatus 102 has a reaction chamber 104 formed in a cylindrical shape such as stainless steel, and the reaction chamber 104 is grounded. An exhaust port 108 is provided at the bottom 106 of the reaction chamber 104 for exhausting the air flow in the container. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) --------- pack- ----- 1T ------ 0 (Please read the precautions on the back before filling out this page) 23 554382 A7 ___ _B7 V. Description of the invention (21) A connection is provided at the exhaust port 108 The exhaust system 112 'of the evacuation pump 110 allows the inside of the reaction chamber 104 to be uniformly evacuated from the bottom peripheral portion. A circular plate-shaped mounting table 116 is provided in the reaction chamber 104 via a pillar 114 made of a conductive material, and a semiconductor, for example, can be placed on the upper surface. Specifically, 'the mounting table 116 has the function of a lower electrode, and the mounting table 116 is composed of a lower table 116A which can be directly supported by a pillar and an upper table 116B which is connected to the upper surface of the lower table Π6A, and is connected at the joint. A resistance heater 118 is interposed between the surfaces. The lower stage 116A and the upper stage 116B are joined at the joint surface by, for example, welding. At the top of the reaction chamber 104, a top plate 122 integrally provided with a shower head 120 serving as an upper electrode is air-tightly installed on the side wall of the container with an insulating material 124 as an intermediary. The shower head 120 is relatively arranged to cover the mounting platform Π6 in a nearly comprehensive manner, and a processing space S is formed between the shower head and the mounting platform 116. The lotus head 120 is used to introduce various gases into the processing space s in a spraying manner. A plurality of spray holes 128 for spraying the gas are formed at the spray surface 126 below the shower head 120. In addition, the shower head 120 is provided with a diffusion plate 132 having a plurality of diffusion holes 130 inside, which can be used to diffuse gas. A gas introduction port 134 for introducing gas into the head is provided at the upper part of the shower head 120, and a gas supply passage 136 is connected to the gas introduction port 134 to allow gas to flow. The fork tubes 138 branched from the supply path 136 are each connected: a TiCl4 gas source 140 capable of storing tritium-containing gas such as TiCl4, a silane source 142 capable of storing SiH4 gas as a silane-based gas, and a tritium source capable of storing N2 gas 144, Ar gas source that can store plasma gas, such as Ar gas, 146, storable additive gas (reducing gas), such as Krypton 2 gas, Krypton 2 gas source 147 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) --'-- r-: ---__ (Please read the notes on the back before filling out this page) Order the printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 24 554382 A7 B7 V. Description of Invention (22). Here, the flow rate of each gas is controlled by a flow controller, such as a mass flow controller 148, provided in the respective fork pipe. In addition, the silane-based gas system is not limited to silane, but can also be used as disilane, dichlorosilane, and the like. As the reducing gas, NH 3 gas may be used. The ceiling 122 is connected to the matching circuit 152 and a high-frequency power source 154 for a plasma having a specific frequency such as 13.56 MHz through a wire 150 to form a plasma when a TiSiN film is formed. Furthermore, a gate valve 156 is provided on the container side so that it can be hermetically opened and closed during wafer loading and unloading. Also, although not shown, it is also known that a wafer lifting pin which can support and lower the wafer during loading and unloading is provided on the mounting table. Next, a method for forming a barrier metal layer and a wiring layer 172 made of a TiSiN film on the semiconductor wafer W on which the interlayer insulating film 162 and the contact channel 160 are formed will be described with reference to FIGS. 13 and 14 (a). First, a semiconductor wafer W is introduced into the reaction chamber 104 through the opened gate valve 156, the wafer W is placed on the mounting table 116, and the reaction chamber 104 is sealed. As shown by circle 14 (A), in the previous step, an interlayer insulating film 162 is formed on the surface of the wafer W, and the interlayer insulating film 162 is already formed to contact the transistors on the wafer. Contact channel 160 and so on. If the inside of the reaction chamber 104 has been sealed, SiH4 gas, tritium gas, TiCl4 gas can be used as the working gas, Ar gas can be used as the plasma gas, and H2 gas can be used as the additive gas. The inside is introduced, and the inside of the reaction chamber 104 is evacuated by a vacuum pump 110, and maintained at a predetermined pressure. In addition, the TiCl4 gas system uses room temperature as the paper standard and applies the Chinese National Standard (CNS) A4 (210X297 mm). ^-(Please read the precautions on the back before filling this page.) Printed by Gongbo Bone Cooperatives 25 Printed by Gongxiao Bone Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs, 554382 A7 B7 V. Description of Invention (23) The liquid can be heated and gasified and supplied to the reaction chamber 104. In addition, the pipes from the TiCl4 gas source 140 and the TiCl4 to the reaction chamber 104 and the mass flow controller 148 are heated by a heating device (not shown) to prevent the TiCl4 gas from condensing. Furthermore, the top plate 122 and the reaction chamber wall of the reaction chamber are also heated. At the same time as the aforementioned operation, a high-frequency power source 154 is used to apply a high-frequency of 13.56 MHz to the shower head 120 of the upper electrode, so that a high-frequency electric field is applied between the shower head 120 and the mounting table 116 of the lower electrode. Thereby, the Ar gas is plasmatized, and the TiCl4 gas, H2 gas, SiH4 gas, and gas are reacted to form a TiSiN film on the wafer surface by plasma CVD. The temperature of the wafer W is maintained at a predetermined temperature by the resistance heater 118 embedded in the mounting table 116. The working conditions at this time are preferably within the following ranges.

Wafer temperature: 350 ~ 450 ° C Operating pressure: 0.5 ~ 5Torr High frequency: 13.56MHz

High-frequency power: 200 ~ 800W

TiCl4 gas flow: 1 ~ lOsccm H2 gas flow: 100 ~ 2000sccm 乂 Gas flow: 30 ~ 500sccm

SiH4 gas flow rate: 0.1 ~ lOsccm Among which, setting the wafer temperature to 350 ~ 450 ° C is that when the temperature is lower than 350 ° C, the C1 concentration of the TiSiN film can be increased, and there is a problem that the upper layer Cu is etched. When it is greater than 450 ° C, when a Cu layer is present at the base of the TiSiN film, Cu diffuses into the TiSiN during the film formation process, which impairs the barrier properties of the TiSiN film. In addition, for other operating conditions, the paper size in the experimental examples described below applies the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) II .--: ί | 丨 ^ ------ order --- -*-I # 1 (Please read the notes on the back before filling out this page) 26 554382 Printed by the Ministry of Irrigation and Wisdom / | ^; ^ 工 4 赀 Cooperatives A7 B7 V. Description of Invention (24) Further explanation. FIG. 14A is an enlarged view showing a contact channel 160 before a TiSiN film is formed on the surface of the semiconductor wafer W. FIG. The contact channel 160 is opened toward the interlayer insulating film 162 made of SiO2, and the silicon surface of the diffusion layer 164 is exposed at the bottom. The wafer W is composed of a silicon single crystal substrate, and the diffusion layer 164 is formed into a silicon layer or a dream-containing layer. In addition, as shown in FIG. 14B, on such a wafer surface, plasma CVD film formation is performed under the aforementioned operating conditions. Needless to say, on the wafer W, titanium is formed on the sidewall and the bottom of the contact channel 160. A silicon nitride film (TiSiN film) 166. According to this, after the TiSiN film 166 having a predetermined thickness is formed by plasma CVD, the wafer W is transferred to another film forming apparatus, and the first copper layer 168 is formed very thinly by a common CVD operation, for example. As a seed layer, the aspect ratio of the contact channel is reduced. Next, copper is deposited on the upper surface by sputtering or electroplating, and the contact channel 160 is buried. At the same time, a second copper layer 170 is deposited on the surface of the interlayer insulating film 162 to form a wiring layer 172 (refer to Section 14 (C) above). ) Figure). In this way, by providing a TiSiN film 166 as a barrier metal layer between the silicon layer or the silicon-containing diffusion layer 164 and the copper layers 168 and 170, even if the TiSiN film 166 is very thin, it can exert the effect as a barrier and prevent Suction silicon and copper diffusion to the silicon layer side. In addition, by appropriately selecting the composition of the TiSiN film 166, the barrier properties can be increased, and a resistivity such as 500 to 5000 μΩ (: πm) TiSiN film required in current or future design rules can be obtained. Resistivity within the range, each cost paper size in TiSiN film is applicable to China National Standard (CNS) A4 specification (210X297 mm) --------- install ------ iT ----- -0 (Please read the precautions on the back before filling this page) -27-554382 A7 _____ Β7 V. Description of the invention (25) The composition system of Ti, which is in the range of 10 ~ 40at%, and Si which is in the range of 10 ~ 40at Within the range of%, N is preferably in the range of 25 to 47 at%. In addition, before the TiSiN film is formed, a Ti film or a titanium silicide film can also be formed. Thus, a Ti film or a titanium silicide film can be formed as the TiSiN film. The resistivity can be reduced to 100 μ cm. To change the composition of the components in the TiSiN film, it is only necessary to change the supply amount of at least one of siH4 gas, N2 gas, and H2 gas. The following is a detailed description of this point. 15th line shows the relationship between SiH4 gas flow rate and resistivity Rs; 16th line shows > The circle of the relationship between the flow rate and the resistivity Rs of the 12 gas; the circle Π shows the relationship diagram of the flow rate and the resistivity Rs of the 112 gas. From the above line graph, it can be seen that an increase in silane gas (SiH4 gas) or tritium When the supply amount of H2 gas is reduced or the supply amount of H2 gas is decreased, the resistivity of the TiSiN film can be increased, and the TiSiN film having a resistivity in the range of 5000 to 5000 μ Ω cm can be easily realized. The flow rate of each other gas in the line 15 ~ 17 is set to a predetermined value within the range of the aforementioned gas. When printed by the Industrial and Commercial Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to adjust the resistivity, H2 gas and N2 gas can be changed The flow rate 'must then be adjusted for other gas flows. In contrast, when changing the flow rate of Sil · ^ gas, it is not necessary to adjust the flow rate of other gases, so it can be made easy to operate and control. The present invention will be described in detail. [First Experimental Example] The film formation experiment of TiSiN film is performed as the following operating conditions (film formation conditions) are changed. This paper size applies Chinese National Standard (CNS > A4) Grid (210X297 mm) 28554382 Intellectual Property Office ❺ Economic Co-op main printed Α7 Β7 V. Description of the Invention (26) wafer temperature: 400 ° C (- constant) Pressure: ITorr, 3Torr

TiCl4 gas flow: lOsccm (—fixed)

H2 gas flow: 100sccm, 2000sccm Ar gas flow: 100sccm, 500sccm, 1000sccm N2 gas flow · 100sccm, 200sccm, 500sccm SiH4 gas flow: Osccm, lsccm, 2sccm, 5sccm High frequency power: 200W, 500W High frequency: 13 · 56MΗζ (—determining) Based on the aforementioned operating conditions, the selection of the best suitable conditions is mainly based on the content of Cl in the TiSiN film and the resistivity of the TiSiN film. It is known from the results that under the following operating conditions:

Wafer temperature: 40 (TC operating pressure: 3Torr

TiCl4 gas flow: lOsccm H2 gas flow: 2000sccm

Ar gas Zhao flow: lOOsccm thoron gas flow: 500sccm

SiH4 gas flow: 5sccm High-frequency power: 500W High-frequency frequency: 13.56MHz, the best value can be obtained, that is, the content of Cl in the TiSiN film is 6.7at%, and the resistivity is 1880μΩ cm. It is a standard film forming condition (STD). This paper size applies the Chinese National Standard (CNS) M specification (210X29 * 7mm) ^ 1T. ^ (Read the precautions on the back before filling this page) -29-554382 A7 B7 V. Description of the invention (27) ( Please read the notes on the back before filling this page.) In addition, the content of Ti in the TiSiN film is 30at%, the content of Si is 23at%, and the content of N is 31at%. In addition, the step recovery is 20 ° / when A / R = 3 (At this time, A refers to the channel diameter, which is 0.6 μιη (0); R refers to the channel depth, which is 1.8 μm). , 13% at A / R = 4. Fig. 18 is a detailed plot of the relationship between the SiH4 gas flow rate and the resistivity of TiSiN shown in Fig. 15; Fig. 19 is a graph showing the composition ratio of the TiSiN film at this time. It should be noted that the vertical axis of the line graph shown in Fig. 18 is not a logarithmic punctuation point, but a normal scale. The operating conditions required for the film formation experiments used to obtain the data in Figures 18 and 19 are shown in the standard conditions except for SiH4 gas, and the SiH4 gas flow rate was changed from 1 to 10 sccm. The resistivity of the TiSiN film obtained at this time is in the range of 500 to 100 μm cm. At this time, as shown in Fig. 19 (a), the composition ratio of Si increases as the flow rate of the SiH4 gas increases. Conversely, the composition ratio of Ti and N decreases. The reason why the resistivity rises simultaneously with the increase in the SiH4 gas flow rate is the increase in the S—N bond in the TiSiN film. Secondly, based on the aforementioned standard conditions, the flow of silane was changed from 0, printed by 1, 2, and 5 sccm of the Industrial and Commercial Intellectual Property Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs to discuss the S—N bonding of the TiSiN film during film formation. status. The results are shown in FIG. 20. When the 20th data was obtained, ESCA (Electron Spectroscopy Analysis) was used. Here, the material of the thermal nitride film (Si3N4) of silicon as a reference sample of Si-N combination and the material of the thermal oxide film (Si02) of silicon as a reference sample of Si-0 combination are combined and recorded. In the line graph, the horizontal axis is the binding energy (eV) and the vertical axis is the photoelectron intensity. '' This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 30 554382 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Industrial and Consumer Cooperative A7 B7 V. Description of the invention (28) As can be seen from the line chart in Figure 20, When a TiSiN film formed using SiH4 gas has peaks P5, P2, and P1 at the same positions as the peaks of the Si-N reference sample (Si3N4), the existence of Si-N bonds can be confirmed. In addition, it was also confirmed that when the flow rate of silane was increased, the peak value was increased, and the ratio of Si ″ N was also increased. Especially when the flow rate of SiH4 gas is 5 sccm, it can be confirmed that the display has a sharp peak. Furthermore, X-ray diffraction was used to discuss the amorphous nature of the TiSiN film formed under the aforementioned operating conditions. The obtained results are shown in the graph of FIG. 21, and the horizontal axis of the graph refers to the diffraction angle. If the TiSiN film is crystalline, the peaks of the TiN (200) alignment should be in the range of 30 to 60 °, but no peaks appear in each film, so it can be confirmed that all of them are amorphous. In this way, it can be seen that the TiSiN film is not crystalline but amorphous. Therefore, the resistance is also not very high as described above, and the TiSiN film can be formed into a film with high barrier properties. Next, an evaluation of the barrier property of the barrier metal layer made of a TiSiN film was performed, and the result was shown. The evaluation of the barrier property refers to: forming a 400A or 100A TiSiN film on a silicon substrate under the aforementioned operating conditions (SiH4 is 5 sccm), and further forming a 2000A Cu film on the silicon substrate, followed by firing at a temperature of about 500 ° C At 30 minutes, discuss the diffusion of copper, titanium, and silicon. FIG. 22 shows a diffusion state when the TiSiN film is 400A. The horizontal axis of the line circle refers to the depth direction of the silicon substrate. From the line graph, it can be confirmed from the distribution of Cu concentration along the depth direction of the silicon substrate that when the TiSiN film is 400A, Cu hardly diffuses toward the silicon side, and silicon does not diffuse toward the Cu layer side. Therefore, it was confirmed that the barrier property of the TiSiN film was extremely high. In addition, for TiSiN films with a film thickness of about 100A, the Chinese paper standard (CNS) A4 (210X297 mm) applies to this paper size --------- ¢ ------ 1T ----- -^ (Please read the notes on the back before filling this page) -31-554382 A7 B7 V. Description of the invention (29) (Please read the notes on the back before filling this page) Perform the same measurement, and the results can also be used It was confirmed to have the same sufficient barrier properties as described above. In the line drawing, it seems that titanium diffuses toward the Cu layer, but in reality, this is only an error in the characteristics of the measured value. Actually, there is no diffusion. This part is indicated by "not true". Fig. 23 is a TEM (Transmission Electoron Microscopy) photograph showing the cut surface of the film when the film thickness of the TiSiN film is 100A. As shown in the photograph, the arrangement of atoms is not visible on the TiSiN film, and an amorphous state is formed. Furthermore, Cu does not penetrate the TiSiN film and diffuse toward the Si side, forming a good state. [Second Experimental Example] As will be described later, a variety of TiSiN films having different film compositions were made by changing operating conditions, and experiments were performed to evaluate heat resistance. The experimental sample refers to a case where a TiSiN film is formed on a Si wafer, and a Cu film is further formed on the TiSiN film. Film formation conditions 2-a (STD) Wafer temperature: 400t: Operating pressure: 3Torr Intellectual Property Bureau of the Ministry of Economic Affairs

TiCl4 gas flow: lOsccm H2 gas flow: 2000sccm

Ar gas flow: 100 sccm > 12 gas flow: 500 sccm

SiH4 gas flow: 5sccm High frequency: 13.56MHz

High-frequency power: 500W This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 32 554382 A7 B7 V. Description of the invention (30) Film formation bar 侔: The difference in film formation conditions is that the SiH4 gas flow rate is changed 3 sccm, the rest are the same as the film formation conditions 2-a. The film forming conditions 侔 2-c are different from the film forming conditions: the SiH4 gas flow rate is changed to 5 seem 'the operating pressure is changed to 3T0ΓΓ (this is the same as the condition 2-a), and the rest are the same as the film formation conditions 2- a is the same. The experimental samples obtained under each film formation condition 2-a ~ 2-c were calcined at 60 ° C or 700 ° C, and the composition of the TiSiN film after calcination was compared with the composition immediately after film formation. The results are shown It is shown in Table 1. --------- Installation I (Please read the precautions on the back before filling in this page. Intellectual Property Bureau of the Ministry of Economic Affairs a (Industrial and Consumer Cooperative Printed Film Condition Condition Film Composition (at%)) Ti Si NC immediately after film formation 30.4 20.9 31.9 7.4 z,-α (STD, 600 ° C after calcination 31.2 21.8 28.9 7.0 LU) 700 ° C after calcination 29.0 23.1 27.9 7.2 immediately after film formation 29.0 19.4 39.5 3.7 2- b After calcination at 600 ° C 29.7 23.0 35.4 1.5 After calcination at 700 ° C 28.7 29.3 35.0 1.1 After film formation 11.3 36.2 44.8 3.4 2-c After calcination at 600 ° C 11.2 37.0 44.0 3.3 After calcination at 700 ° C 10.3 37.0 43.8 2.8 It can be seen from Table 1 that according to any of the film formation conditions, the composition of the TiSiN film has a tendency of N to decrease (because N is detached from the film by heat) and Si to increase (due to substrate absorption). The tendency is the order in which the film formation conditions 2-b, film formation conditions 2-a, and film formation conditions 2-c are decreased. That is, the paper conditions applicable to the film formation conditions 2_〇 are applicable. China National Standard (CNS) A4 specification (210X297 mm) Line 33 Intellectual Property Bureau of the Ministry of Economic Affairs: Printed by Beigong Consumer Cooperative 554382 A7 B7 V. Description of the invention (31) The TiSiN film composed of the obtained film has the best heat resistance. [Third Experimental Example] As described later, when the high-frequency frequency during film formation was set to 60 MHz, experiments were performed to confirm the change in the film composition of the TiSiN film. Film-forming conditions 3-a The film-forming conditions differ in the high-frequency The frequency is set at 60MHz, and the other conditions are the same as film formation condition 2-a (STD). Film formation condition 3-b The film formation conditions are different in that the operating pressure is set to ITorr, SiH4 gas flow rate 7sccm, and the high-frequency frequency 60MHz, and the rest The conditions are the same as the film formation conditions 2-a (STD).

The composition of the TiSiNi film obtained by the foregoing two conditions is shown in Table 2. Table 2 Film formation conditions Film composition (at%) Ti Si N Cl 3-a 18.9 21.3 32.2 20.5 3-b 38.7 10.5 33.3 12.2 In addition, for standard film formation conditions 2-a, only film formation conditions with different high-frequency frequencies 3 -a is because the resistance value of the film is too high (80200 μ Ω cm), it is known that it is not suitable for a barrier layer. In addition, when the film is formed under each of the film forming conditions 3-a and 3-b, the Cl concentration in the TiSiN film is increased, so it is not suitable for use as a barrier layer. However, under film formation conditions 3-b, the step recovery (at A / R = 3) was 30%, which was a good one. [4th experimental example] This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) --r-: --.-- ΓΛ ------ 1T ---- ^-( Please read the notes on the back before filling in this page) 34 554382 Intellectual Property Bureau of the Ministry of Economic Affairs only. Printed by Industrial Cooperative Bone Cooperative A7 B7 V. Description of Invention (32) Experiments will be performed as described below to change the flow of N2 gas during film formation. Confirm the change in the composition of the TiSiN film. Film formation conditions 4

Wafer. Temperature: 400 ° C Operating Pressure: 3Torr

TiCl4 gas flow: lOsccm 1 ^ 2 gas flow: 2000sccm Ar gas flow: lOOsccm N2 gas flow: lOOsccm

SiH4 gas flow: 3, 4, 5sccm, high frequency: 60MHz

High-frequency power: 500W Also, the above-mentioned film formation condition 4 is different in that the 1 < 2 gas flow rate is 100 sccm, which is lower than the standard film formation conditions; and the SiH4 gas flow rate is changed to 3, 4, 5 sccm. The rest are the same as the standard film formation conditions (STD).

The composition of the TiSiN film obtained under the foregoing three conditions is shown in Table 3. Table 3 5 outflow (seem) Membrane composition (at%) Ti Si N Cl 3 34.0 32.6 26.7 3.4 4 28.5 37.6 26.6 4.1 5 21.8 44.5 25.1 4.6 As can be seen from the description in Table 3, by setting the flow rate of N2 gas to 100 sccm Compared with standard film forming condition 2-a, the Cl concentration in the TiSiN film can be reduced by 1/2. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) --------- Select ------ 1T ------ 0 (Please read the precautions on the back before (Fill in this page) -35 554382

It is also known that when the SiH4 gas flow rate is increased, the Ti concentration in the TisiN film can be reduced, and the Si concentration can be increased. This is because the reaction amount in the TiSi direction is promoted because the amount of the film formation gas is reduced. [Fifth experimental example] The SiH4 gas flow rate was fixed at 1, 2, and other operating conditions such as the following conditions were fixed to discuss changes in film composition. 4. Change between 5 and 5 sccm, and simultaneously form the TiSiN film to determine the film conditions. 5 Wafer temperature Operating pressure TiCl4 gas flow rate Specific gas flow rate Ar gas flow rate Gas flow rate High frequency frequency High frequency power

400 ° C 3Torr lOsccm 2000sccm 500sccm 500sccm 13.56MHz 500W The composition of the TiSiN film obtained through the above three conditions is shown in Table 4 II 1— II J1 I- 1!! I-I (Please read the note on the back first and then Fill out this page} Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

5 Old 4 flow (seem) Membrane composition (at%) Ti Si N Cl 1 40.4 4.5 40.0 10.3 2 36.4 9.7 38.3 9.9 3 32.1 14.6 37.8 8.7 4 27.1 20.5 36.2 8.2 5 30.4 22.8 31.2 6.5 This paper scale is applicable to Chinese national standards ( CNS) A4 specification (210X297 mm) 36 554382 Member of Intellectual Property Bureau of Ministry of Economic Affairs X printed by A7 B7 V. Description of the invention (34) By setting the N2 gas flow rate higher than the film formation condition 4, the standard film formation conditions are equivalent At 500sccm, C1 in TiSiN film with a content of 3.4 ~ 4.6% can be increased to 6.5 ~ 10 · 3% under film forming condition 4. In addition, by increasing the flow rate of SiH4 gas, the reduction effect of SiH4 can be used to reduce the C1 concentration, and the (: 1 concentration is much higher than that under film formation condition 4 where the N2 gas flow rate is 100 sccm. [6 Experimental Examples]

First, a 100-A-thick TiSiN film was formed on a Si wafer. TiSiN film refers to: standard TiSiN film (meaning TiSiN film obtained through standard film forming conditions); TiSiN film with more TiSi; TiSiN film with more TiN; TiSiN film with more SiN. The standard TiSiN film is obtained through film formation conditions 2_a (standard film formation conditions). A TiSiN film with a large amount of TiSi is obtained by changing the N2 gas flow rate to 100 sccm under film formation conditions 2-a (standard film formation conditions). In addition, a TiSiN film having a large amount of TiN is obtained by changing the H2 gas flow rate to 3000 seem in film formation condition 2-a. In addition, a TiSiN film with a large amount of SiN is obtained by changing the TiCl4 gas flow rate to 3 sccm under film formation conditions 2a. Next, Cu is formed on the TiSiN film. The film formation of Cu is performed by sputtering. The operating conditions are: operating pressure 0.67pa, high-frequency power 500W, reverse sputtering 200W for 2 minutes, preliminary sputtering for 5 minutes, and Ar gas flow 20sccm to form Cu with a film thickness of 3000A. , As the target 4N purity of Cu. Secondly, the calcination was performed in a vacuum (5x10 · 6Tοτ) at a calcination temperature of 550 ° C or 600 ° C for 30 minutes (this time refers to the elapsed time after the environment in which the sample was placed actually formed 5x10 · 6Tοτ). The heating rate during calcination is set to 10 to 20 ° C / min, and the cooling rate is 5 to 10eC / min. In addition, this paper size applies Chinese National Standard (CNS) A4 specification (210X29 * 7mm). I line (please read the precautions on the back before filling this page) • 37-554382 A 7 B7 V. Description of the invention (35 ) Make another unburned sample for comparison. (Please read the precautions on the back before filling this page.) Table 5 shows the composition and resistivity of the TiSiN film immediately after film formation, and the barrier results of Cxi after calcination. Film composition (at%) Resistivity (μΩαη) Cu barrier Ti Si N Cl 550 ° C Calcination 600 ° C Calcination STD 30.4 22.8 31.2 6.5 1676 Good TiSi-rich 29.3 45.4 19.6 2.9 420 Good and bad TiN-rich 38.1 17.4 31.8 8.6 245 Liangliang SiN-rich 16.3 34.8 36,5 4.1 675000 Liangliang. The barrier properties evaluated in Table 5 are easily understood by referring to the line in Figure 24. Printed by the Intellectual Property Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs and using the SIMS (Secondry Ion Mass Spectroscopy) to compare and discuss the diffusion of Cu into Si wafers in Si wafers with standard TiSiN films and TiSiN films with more TiSi. Shown at 25th. From the circle of the 25th line, it can be seen that Cu does not diffuse toward Si in a standard TiSiN film, and the barrier property is better. On the other hand, in a TiSiN film with a large amount of TiSi, Cu diffuses into Si, indicating that the barrier property is poor. The reason for such a difference is described later. Cu diffusion is carried out by grain boundary diffusion and intra-grain diffusion, while grain boundary diffusion is dominant. It is conceivable that in a TiSiN film with a large amount of TiSi, the TiSiN film is crystallized by calcination, so that grain boundary diffusion is likely to occur. On the other hand, since the standard TiSiN film is amorphous, it is found that it is difficult to cause Cu diffusion. This paper scale applies Chinese National Standard (CNS) A4 specification (210X297 cm) 38 554382 A7 B7 112 gas flow Ar gas flow > 12 gas flow surface frequency power high frequency frequency 5. Description of the invention (36) Borrowing from the above experimental results, When the operating pressure is set to 3 Tοτ (high pressure), from the viewpoint of the Cu barrier property of the obtained TiSiN film, the film formation conditions are preferably set to the following matters, namely: Wafer temperature: 400 ° C TiCl4 gas flow rate : LOsccm 2000sccm lOOsccm 500sccm 500W 13.56MHz Also, at this time, the SiH4 gas flow rate is preferably set to 1 ~ lOsccm, and 5sccm is the best. From the viewpoint of Cu barrier property, it can be known that the composition of the TiSiN film is preferably 28 to 31 at% Ti, 20 to 25 at% Si, and 28 to 32 at% N, while Ti is 30 at% and Si is 23 at. %, N is 31at% is the best. [Sixth experimental example] In this experiment, the change in the film composition of the TiSiN film when the operating pressure is reduced to 0.6 Torr is discussed. Film formation conditions 6-a Wafer temperature: 40 (rc Operating pressure: 0.6 Torr Ding 1 (: 14 gas flow rate: 2 sccm) 仏 Gas flow rate: 500 sccm Ar gas flow rate: 50 sccm This paper is in accordance with China National Standard (CNS) A4 specifications (210X297mm) --------- ¢ ------ IT ------ 0 (Please read the notes on the back before filling this page) Ministry of Economic Affairs Finance 1 Bureau: HX4 fee Co-operative printed 39 554382 A7 B7

0 · 1, 0 · 2, 0.3, 0.5 or l.Osccm 13.56MHz 500W Invention description (37 N2 gas flow: 50sccm SiH4 gas flow South frequency frequency high frequency power The results are shown in Table 6 and Figure 26. 81 (seem) _ 1 guest composition (at%) resistivity (μ Ω cm) Remarks Ti Si N Cl 0 48.6 37.4 3.6 593 Step recovery 40% (A / R = 4) 〇7l 36.2 11.6 44.5 2.5 1313 33.9 13.0 45.2 3.0 1994 6.3 30.2 16.7 44.7 3.0 3380 0.5 24.1 22.3 45.7 3.2 8268 Γ〇 ~ 16.2 29.8 47.2 3.6 284000 Film-forming strips (please read the precautions on the back before filling this page) The difference between the film-forming conditions 6-b is that · Set the gas flow rate of n2 to 30, 40, 50, or 80secm, and set the gas flow rate of 8 cases to 0 sccm (constant). The rest is the same as the film formation condition 6-a. The results are shown in Table 7. Table 7 7 \ Flow (seem) 1 Mo composition (at%: resistivity (μΩαη) Ti Si N Cl 30 32.3 13.8 46.3 2.8 2374 40 1 33.1 13.7 46.3 2.2 2457 50 31.9 14.7 46.5 2.6 3029 80 32.1 14.6 46.1 2.5 2881 Film formation conditions 6-c Film formation conditions 6-c differs in that the cardiac gas flow rate is set to 30, 500 or 70〇sccm, and set the SiH4 gas flow rate to 0.2sccm (—the paper size is set to the Chinese National Standard (CNS) A4 specification (210X297 mm) # 1. Ministry of Economic Affairs ir & w / i bureau a (printed by Industrial and Consumer Cooperative) 40 554382 A7 B7 Printed by the AV Industry Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (38), the rest are the same as the film formation conditions 6-a. The results are shown in Table 8. H2 flow (seem) ί Its composition ( at%) Resistivity (μ Ω cm) Ti Si N Cl 300 29.6 17.3 47.4 1.9 7514 500 31.9 14.6 46.5 2.6 3029 700 32.9 13.3 46.8 2.7 2772 It can be known from the foregoing experimental results whether the film formation pressure is high (3Torr) Up to the setting of low pressure (〇 · 6Τογγ), according to the decrease of TiCl4, Ar, N2 and SiH4 gas flow, the concentration of Cl in the SiN film can be reduced (to 1.9 ~ 3.0%), and the barrier property of Cu can be made. And step recovery is good (40% at A / R = 4). In particular, when the flow rate of the H2 gas is set to 300 sccm, the C1 concentration in the TiSiN film can be reduced to less than 2%. [Seventh Experimental Example] First, through film formation conditions 6-a (four conditions, such as SiH4 gas flow rate set to 0.1, 0.2, 0.3, or 0.5), each was formed to form a 200A TiSiN film on Si crystal®. sample.

Next, a Cu film was formed on the TiSiN film for each sample. The film formation of Cu is performed by sputtering. The operating conditions are 0.67Pa, high-frequency power 500W, reverse sputtering 200W for 2 minutes, preliminary sputtering 5 minutes, and Ar gas flow 20sccm to form Cu with a film thickness of 3000A. Membrane, Cu as target 4N purity. Subsequently, a part of the sample was prepared at a wafer temperature of 400 ° C, a working pressure of 0.6 Torr, an H2 gas flow rate of 500 sccm, an N2 gas flow rate of 50 sccm, an Ar gas flow rate of 50 sccm, a high-frequency frequency of 13.56 MHz, and a high-frequency power of 500 W. Applicable to Chinese National Standard (CNS > A4 specification (210X297 mm) --------- install ------ 1T ------ line (please read the precautions on the back before filling in this (Page) 41 554382

7 7 A B V. Description of the invention (39) Plasma treatment is performed under the conditions (hereinafter referred to as "post-plasma treatment"). (Please read the precautions on the back before filling out this page.) Then, for all samples, the calcination temperature is 550 ° C or 600 ° C for 30 minutes in a vacuum (5 × 10 · 6Τογγ) (this time refers to The elapsed time after the sample was placed in the environment where 5 × 10 · 6Tη was actually formed). In addition, the heating rate during calcination is set to 10 to 20 ° C / min, and the cooling rate is 5 to 10 ° C / min. ○ With regard to the sample thus obtained, the composition, etching resistance, and barrier properties of the TiSiN film are discussed. , Resistivity of TiSiN film. Results are shown in Figure 27 and Table 9 Table 9

SiH4 flux (seem) Film composition (at%) Etching barrier Ti Si N Cl 550 ° C Calcination 600 ° C Calcination plasma treatment + TiS_ 550 ° C Calcination 550 ° C Calcination 600 ° C Calcination electricity Slurry treatment + TiSi ^ N film 55 (TC calcination 0 48.6-37.4 3.6 Yes Yes Yes Goodness 0.1 36.2 11.6 44.5 2.5 Yes Yes Yes Goodness 0.2 33.9 13.0 45.2 3.0 No Yes No Bad bad 0.3 30.2 16.7 49.7 3.0 No No good and bad bad 0.5 24.1 22.3 45.7 3.3 No good and bad bad good 1.0 16.2 29.8 47.0 3.0 Slightly no good and good Liang Xiaoliang Consumer Goods Bureau of the Ministry of Economic Affairs and Intellectual Property Bureau printed it for burning at 550 ° C, blocking The performance is not good when the flow rate of SiH4 gas is 0.2sccm and 0.5sccm, but it is good when the flow rate of SiH4 gas is Osccm, 0.1 seem, and 0.3seem. Moreover, when the temperature is 600 ° C, the barrier property is in SiH4 gas. When the flow rate is 0.2 sccm, 0.3 sccm, and 0.5 sccm, it is not good, but the flow rate of 4 gas at 8 out of 5 (: (: 111, 0.15 (: (: 111 and 1.05): (: good for 111) The paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 42 554382 A7 B7, Bureau of Intellectual Property of the Ministry of Economy-Ministry of Economics; a X Consumer Cooperative printed 1 ^ 2 gas flow Ar gas flow 乂 gas flow high-frequency power high-frequency frequency 5. Description of the invention (40) Also, the flow rate of SiH4 gas is 0.5sccm and l.Osccm, the resistivity becomes very high, and it is not suitable for use as a barrier film. Also, when the flow rate of SiH4 gas is Osccm, the C1 concentration in the TiSiN film is very high, which is 3.6%, and the corrosion resistance is poor, so it is not suitable. The TiSiN film obtained when the flow rate of SiH4 gas is 0.1 sccm is the best under the conditions of barrier property, corrosion resistance and low resistance. It is also known that the resist surface of the TiSiN film even when the film is just formed When there are some problems, the post-plasma treatment can be used to obtain a film with excellent corrosion resistance. In addition, according to the experimental results shown in Table 9, when the operating pressure is set to 0 · 6Tογγ (low pressure), From the viewpoint of the Cu barrier property of the TiSiN film, the film formation conditions are preferably set to the following, namely: Wafer temperature: 40 (TC TiCl4 gas flow rate: 2sccm 500sccm 50sccm 50sccm 500W 13.56MHz It can also be known that the SiH4 gas flow rate at this time Set to 0.1 ~ 1 seem is better, 0.1 ~ 0.5sccm is better, and 0.1 ~ 0.2sccm is better. In addition, from the viewpoint of Cu barrier property, it is known that the composition of the TiSiN film is preferably 24 to 36 at% Ti, 11 to 22 at% Si, and 44 to 46 at% N, while Ti is 34 at ° / 〇, and Si is 13at%, N is 45at% is the best. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) --------- install ------ 1T ------ line (please read the precautions on the back first) (Fill in this page) 43 554382 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial and Consumer Cooperatives A7 B7 V. Description of the invention (41) Comparison of component numbers Α ·· Β ··. C ··· ......… in the channel department Η Thickness of the film formed on the other part .............. thickness of the film formed on the bottom of the channel ... thickness of the film formed on the side of the channel Η ......... channel section W .... 10 " ...... Thermal CVD 11 .... 11a. ...... Top wall lib .. ...... Bottom wall 12 .. ...... Base 13. ... .... Support member 14 "… … Guide ring 15… ·…. · Heater 16 " …… Power supply 17 ......... Controller 18 " ...... Exhaust pipe 19 .... .Exhaust device 20... Shower head 20a ^ 20b ... gas outlet 30... Gas supply mechanism 31...... C1F3 supply source 32... N2 supply source 33. ... • •… TiCl4 supply source 34 .. …… SiH2Cl2 supply source 35 ..... · NH3 supply sources 39, 40, 41, 42, 43 ......... ...gas 45, 46. Piping 47 .... " ... Valve 48 " ... Mass flow controller 50 .... ..... Si substrate 50a .... Impurity diffusion area 51 .... ..... lower electrode layer 52 .. ...... SiN barrier layer 53....... Insulating layer 54 ..... Upper electrode layer 55... 61 ..… poly-Si plug 62...... Barrier layer 63...… Lower electrode 64...... .. insulation layer (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 44 554382 A7 B7 V. Description of the invention (42) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Consumption Printing Co., Ltd. 65 " ... Upper electrode 66 ... ...... upper electrode 67 ............ lower electrode 68 ...... ... blocking layer 70 ............ Si substrate 70a ......... Impurity diffusion area 71 ........ interlayer insulating film 72 ... ... contact channel 73 ... barrier layer 74 ... metal wiring layer 74a ... buried wiring Portion 80 ... Si substrate 81 " ... Insulation film 82 ... ...... Lower layer 83 ............ Upper layer 83a ... Contact Channel 84 ... Gate electrode 85 ... Spacer 86 ... Wiring layer 87 ... Barrier layer 88 ... Upper layer 89 ... ... gate electrode 90 ... ... source 91 ... ... drain 92 ... SiOxNy film 93. ..... ... insulating layer 94 ... ... barrier layer 95 ... ... upper layer 96 ... ... gate electrode 102 ... Membrane device 104 ......... Reaction chamber 106 ... Bottom 108 ......... Exhaust port 110 ... Exhaust system 112 ... Pneumatic system 114 ..... Pillar 116............ .. Mounting table 116A... ........... Ceiling 124 ... Insulation material 126 ..... Ejection surface 128 ..... Ejection hole 130 ..... Diffusion hole 132 ... · ... diffuser plate 134 ····… gas inlet port binding line (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 45 554382 A7 B7 V. Description of Invention (43) Intellectual Property Bureau of the Ministry of Economic Affairs: Printed by the Industrial and Commercial Cooperatives 136 ... .... Supply path 138 ...… and 140. TiCl4 gas source 142 " ... Silane source 144 " ... N2 gas source 146 ... Ar gas source 147 ..., Η ... 2 gas source 148 ... .... mass flow controller 150 ........., lead 152 ......... matching circuit 154 ... .High-frequency power supply 156 ... .... Gate valve 160 " ... Contact channel 162 ......... Interlayer insulation film 164 ......... Diffusion layer 166 ... • •• • TiSiN film 168 ··· 170 ... 2nd copper layer 172 ... wiring layer (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ) 46

Claims (1)

ABCD VI. Application for Patent Scope No. 88121590 Patent Application Amendment for Patent Scope Revised February 11, 1992 • L A method for manufacturing a film containing TiSiN, which is characterized by including a supply step that will contain a Ti-containing gas, The film-forming gas containing the Si gas and the gas containing the ^ gas is supplied to the reaction chamber; and the film-forming steps are used to contact the aforementioned film-forming gas with the heated substrate placed in the room and heat the CVD in the foregoing A film of TiSiN containing 10 to 40 at% Ti, 10 to 40 at% Si, and 25 to 47 at% N is formed on the substrate. 2 · A method for manufacturing a film containing TiSiN, comprising: a carrying-in step for carrying a substrate into a reaction chamber; and a supplying step 'for supplying a Si-containing gas, a Ti-containing gas, A gas containing N and a reducing gas; a generating step for generating a plasma from a gas containing Si, a gas containing Ti, a gas containing N, and a reducing gas; and a film forming step using the aforementioned plasma on a substrate A film of TiSiN having a composition of 10 to 40 at% Ti, 10 to 40 at% Si, and 25 to 47 at% N is formed. 3. The method of claim 1 or 2, wherein the Ti-containing gas system uses at least one of TiCU, tetrahydroxydimethylamino titanium and tetrahydroxydiethylamino titanium. 4. The method according to item 1 or 2 of the patent application range, wherein the aforementioned Si-containing gas system uses at least one of SiH2Cl2, SiHCl3, SiCl4, SiH4 & Si2H6. 5. The method according to item 1 or 2 of the scope of patent application, in which the above-mentioned N-containing gas system ’s scale is applicable to the China National Standard (CNS) A4 specification (21〇x297 public love 1 ~ ------ -47 -The scope of the patent application uses at least one of NH3 and monomethyl hydrazine. 6. If the method of the scope of patent application is 1 or 2, it further includes the following steps:-a method for supplying the above-mentioned reaction chamber with Η Gas and N-containing gas; one for generating plasma from the aforementioned gas containing rhenium and gas containing N; and one for treating the surface of the aforementioned film containing TiSiN by the aforementioned plasma, so that C1 is removed by the aforementioned film • The method according to item 1 or 2 of the scope of patent application, wherein the aforementioned film containing TiSiIsf is formed on a film layer made of Si or Si02 on the aforementioned substrate in advance. 8 · If applying for a patent The method of the item 1 or 2 of the scope, wherein the film system containing ^^ and ^^ is formed on the film layer composed of Ti or titanium silicide on the substrate in advance. 9 · As in the second item of the patent application scope Method, wherein the aforementioned reducing gas is ^ gas. (2) The method according to the second item of the patent, wherein in the step of supplying the Si-containing gas, the Ti-containing gas, the gas, and the reducing gas into the room, the SiH4 gas as the Si-containing gas is (uqoswm, as the Ti-containing gas). The TiCU gas of the gas is 1 to i0 sccm, and the & gas containing N rolled body is 30 to 500 sccm, and the H2 gas as the aforementioned reducing gas is 100 to 300 sccm, and 100 to 2 〇〇〇 Coffee claws supply Ar gas. 6. Patent application scope 11. Kinds of anti-diffusion membranes composed of TiSiN membranes, which contain 10 ~ 40at% Ti, 10 ~ 4_%, and 25 ~ 47at% 2N. 12. The diffusion prevention film according to item 1 of the patent application scope, wherein the composition of the aforementioned TiSiN-containing film is 28 to 32 at% Ti, 20 to 25 at% Si, and 28 to 32 at ° / 〇N. 13. The diffusion prevention film according to item 丨 丨 in the scope of patent application, wherein the composition of the aforementioned TiSiN-containing film is 24 to 36 at% Ti, 11 to 22 at% Si, and 44 to 46 at% N. 14. Such as The patent application scope of the first anti-diffusion film, wherein the aforementioned film containing TiSiN is a A film for preventing oxygen diffusion. 15. The diffusion preventing film according to item ^ of the patent application range, wherein the film containing TiSiN is arranged between the si layer and the Cu layer. 16. A semiconductor device, the device is characterized by It has a capacitor part. The capacitor part includes: an insulating layer made of a material with a high dielectric constant; a lower electrode layer which is provided below the aforementioned insulating layer; an upper electrode layer which is provided On top of the aforementioned insulating layer; and a barrier layer, which is provided between the aforementioned insulating layer and the lower electrode layer, and is simultaneously composed of Ti containing 10 to 40 at%, 10 to 40% by%, and 25 to 47 at% TiSiN film composed of N, the aforementioned insulating layer composed of high dielectric constant material is composed of (Ba, Sr) Ti03, Pb (Zr, Ti) 03, Ta205 and RuQ At least one of the upper electrode layer and the lower electrode layer formed by one is composed of one of ABCD 554382 VI, patent application scope TiN, TiSiN, Pt, and Ru. 17. A semiconductor device, comprising: a semiconductor substrate; and a gate electrode formed on the surface of the semiconductor substrate with an insulating layer as an intermediary and connected with a wiring layer; and the gate electrode It is a layer composed of a film of TiSiN containing 10 to 40 at% Ti, 10 to 40 at% Si, and 25 to 47 at% N. The gate electrode is mounted by: ordering on the aforementioned semiconductor substrate And an insulating layer formed thereon, which contains one or more selected from the group consisting of a Si02 film, a SiONx film, a (Ba, STi03 film, a Pb (Zr, Ti) 03 film, a Ta205 film, and a RuO film. An insulating layer made of a film, a barrier layer made of a film containing the aforementioned TiSiN formed on the aforementioned insulating layer, and a conductive layer made of a wire made of W, A1, or Cu formed on the aforementioned barrier layer. 18. A method for manufacturing a semiconductor device, characterized by comprising a step for forming a capacitor portion, the step having the following procedures: those for forming a lower electrode layer on a semiconductor substrate; those for forming a barrier layer, The layer A film composed of TiSiN containing 10 to 40 at% of Ti, 10 to 40 at% of Si, and 25 to 47 at% of N on the aforementioned lower electrode layer; for forming an insulating layer, the layer It is attached to the aforementioned barrier layer. It has a high paper size and applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 50 554382 Made of a dielectric constant material; and used to form an upper electrode layer on an insulating layer. 19. A method of manufacturing a semiconductor device, comprising a step of forming a buried wiring portion, the step having the following procedures: a step of forming an insulating layer on a semiconductor substrate or a conductive layer on the substrate; The contact layer or the transfer channel is formed by etching on the foregoing insulating layer; used to form the Si layer containing 10 to 40 at% of Si and 10 to 40 at% on the foregoing insulating layer and in the contact or transfer channel. And a barrier layer composed of a TiSiN ^ film composed of 25 to 47 at% N: and a layer for forming a wiring layer on the barrier layer. 20 · —A film-forming device, comprising: a reaction chamber for receiving a substrate to be processed; a support member for supporting a substrate to be processed indoors; a film-forming gas introduction mechanism, A person for introducing a film-forming gas into the reaction chamber; and a heating mechanism for heating a substrate to be processed supported by the support member; and the film-forming gas introduction mechanism includes a Ti-containing gas, a Si-containing gas, and a The source of N gas. The device is formed on the substrate to be processed heated by the heating mechanism. The device contains 10 ~ 40 at% Ti, 10 ~ 40 at% Si, and Chang's scale. Applicable to China National Standard (CNS) A4. Specifications (210X297 mm) a '_ -51- Binding 554382 A B CD Patent application range 25 ~ 47 at% of TiSiN film of N. 21. The film-forming apparatus according to claim 20, wherein the film containing TiSiN is formed by plasma CVD or thermal CVD. 22. The diffusion prevention film according to item 11 of the application, wherein the aforementioned TiSiN-containing film contains a Si-N bond. 23. The diffusion prevention film according to item 11 of the application, wherein the film containing TiSiN is amorphous. 24. The method of claim 1 or 2, wherein one of the aforementioned Si-containing gas system Si2H6, SiH2Cl2, SiHCl3, and SiH4, the aforementioned reducing gas system nh3 or monofluorenyl hydrazine. 25. The diffusion preventing film according to item 11 of the application, wherein the film containing TiSiN is formed by plasma CVD or thermal CVD. 26. A method for manufacturing a semiconductor device, comprising a step of forming a gate electrode, which includes the following procedures: forming an insulating layer on a semiconductor substrate; and forming 10 to 40 at% on the foregoing insulating layer A barrier layer made of a TiSiN film composed of Ti, 10 to 40 at% Si, and 25 to 47 at% N; and a wiring layer formed on the aforementioned barrier layer. 27. The method according to item 26 of the patent application, wherein the aforementioned insulating layer is formed of one of a Si02 film, a SiONx film, a (Ba, STi03 film, a Pb (Zr, Ti) 03 film, a Ta205 film, and a RuO film. 28. —A method for manufacturing a semiconductor device, characterized in that it includes a step of forming a gate electrode, which includes the following procedures: Gutter This paper is dimensioned to the Chinese National Standard (CNS) A4 (210X297) (Mm) 52 554382 AB CD VI. Application scope: Those who form the i-th insulating layer on the semiconductor substrate; those who have nitrided the aforementioned first insulating layer; formed the high-dielectric constant material on the aforementioned nitrided first insulating layer The second insulating layer is composed of 10 to 40 at% Ti, 10 to 40 at% Si, and 25 to 47 at% on the second insulating layer made of the high dielectric constant material. A barrier layer composed of a TiSiN film composed of N; and a wiring layer formed on the aforementioned barrier layer. Installation 29. The method of item 28 in the scope of the patent application, the aforementioned first insulating layer is made of Si. 2 film structure and 2nd insulating layer It is composed of one of pb (Zr, Ti) 〇; film, film, and RuO film. Order 30. The method of claim 26 or 28, wherein the aforementioned wiring layer is composed of Pt, RU, TiN, and It is composed of one of TiSiN. 31. The method according to item 19 of the scope of patent application, further comprising the step of forming a Ti film or a titanium silicide film before forming the aforementioned barrier layer. The method according to item 2, wherein when the gas containing D1 is used as the gas containing Ti, and the gas containing radon is used as the gas containing Ti, the flow rate ratio of the gas containing Si is 1 to 11 with respect to the flow rate of the TiCU gas, and Relative to the flow rate of the TiCl4 gas, the flow rate ratio of the N2 gas is 4 to 501. 33. As in the method of the second item of the patent application, Ding 14 gas is used as the Ti-containing gas, and tritium gas is used as the gas When the aforementioned N-containing carrier I is used, the flow rate ratio of the TiCl4 gas with respect to the flow rate of the entire gas in the scope of 53 554382 AB c D is 0.00018 to 0.045, and the flow rate ratio of the aforementioned Si-containing gas is 0.00018 0.042, and the flow rate ratio of the aforementioned N2 gas to the flow rate of all the gases is 0.006 to 0.75. 34. For example, the method of claim 18 in the scope of the patent application, wherein the aforementioned lower electrode layer is one of poly Si, Pt, Ru, and TiSiN 35. The method according to item 18 of the scope of patent application, wherein the aforementioned insulating layer is made of at least one of a (Ba, Sr) Ti03 film, a Pb (Zr, Ti) 03 film, a Ta205 film, and a RuO film. Made up. 36. The method of claim 18, wherein the upper electrode is composed of one of Pt, Ru, TiN, and TiSiN. 37. The method of claim 18, further comprising the step of nitriding the aforementioned insulating layer. 38. The method of claim 18 or 19, wherein the TiSiN-containing film is formed by plasma CVD or thermal CVD. 39. A method for manufacturing a film containing TiSiN, comprising the following steps: a step of moving a substrate into a chamber; a step of supplying a gas containing Si, TiCl4 gas, N2 gas, and a reducing gas in the aforementioned chamber; The gas is in contact with the heated substrate placed in the chamber, and by thermal CVD on the substrate, 10 to 40 at% Ti, 10 to 40 at% Si, and 25 to 47 at% N are formed. The film formation step of a TiSiN film composed of 40. If the method of the 39th scope of the patent application is applied, the paper size of the π-line paper is applicable to the Chinese National Standard (CNS) A4 (210X297mm) 54 554382 AB c D SiH2Cl2 gas or SiH4 gas 5 ~ 500 seem, TiCl4 gas 5 ~ 50 seem, NH3 gas 50 ~ 500 seem as the reducing gas, the substrate is heated to 400 ~ 650 ° C; the pressure in the chamber is maintained Those in 0.3 ~ 10 Torr. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 55