TW478096B - Method of silicide formation in a semiconductor device - Google Patents

Abstract

A method of forming a silicide layer in contact with a silicon substrate. The method comprises forming the silicide layer by supplying a silicon-containing source that is different from the silicon substrate, such that the silicon in the silicide layer originates primarily from the silicon-containing source.

Description

V. Description of the invention () Related applications: This application is superior to the commonly designated US Provisional Patent Application No. 60/1 4 1.08, titled "Method for Forming Titanium Silicide Films in Semiconductor Devices" The document was incorporated on June 25, 1999, and is incorporated herein by reference. Summary of the Invention: This method relates to a method for forming silicide in a semiconductor device, and more particularly to a method for forming a silicide layer in contact with a silicon substrate. BACKGROUND OF THE INVENTION: During the fabrication of integrated circuits, an interposer or a transfer layer is often used as a metal isolation layer to block the diffusion of metal to the bottom area under the barrier layer, and / or to enhance the subsequent formation of layers. Adhesion. These bottom areas include transistor gates, capacitor dielectrics, semiconductor substrates, metal wires, and many other structures that appear in integrated circuits. For example, when a dielectric is formed from a transistor, a barrier layer is often used between the material of the gate and the metal layer in contact with the dielectric of the gate. The diffusion barrier layer will block metal from diffusing into the gate material made of polysilicon. -The metal diffusion result is generally not desired because it will change the transistor characteristics or even render it inoperable. For example, a hafnium / nitriding composition can be used as an adhesion / diffusion barrier layer. Second, this isolation stack is also suitable for tungsten (w) quality Behman metallization treatment to contact the source and exhaust area of the transistor. This shield ¥ Tian ^ and the isolation stack can prevent tungsten plugs Page 2 ^ / 8096 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed and description of the invention () and the unwanted metal diffusion between the bottom substrate . For example, the τ i layer is generally deposited on the contact area of a Si substrate, and then the Ti layer is converted into an intermediary TiSix layer, which can provide a lower resistance contact with the Si substrate. And if Ti is deposited using a plasma-enhanced "chemical vapor deposition (PECVD)" method, that is, the temperature is between about 550 and 700 ° C, a reaction will occur between the Ti film and the Si substrate on the bottom contact surface. This will cause a TiSix layer on the Si substrate. In addition, if the Ti thin film is deposited by "physical vapor bonding (PVD)", the bottom contact surface may be subjected to an "individual rapid heat treatment (RTP)" step during earlier or subsequent thin film processing. Ding Yi layer was formed. Next, a TiN layer is formed on the Tisix layer, and then a tungsten (w) plug is formed. In addition to serving as an isolation stack, the TiN layer also serves two functions: 丨) prevents the TiSix chemical attack by tungsten hexafluoride (WF6) during w-mass deposition; and 2) serves as a colloidal layer to improve tungsten quality The adhesion of the plug. The characteristic dimensions of integrated circuit components are currently in the range of about 0.25 micrometers (m). The characteristic dimensions of the new generation of semiconductor elements in the future will fall into the sub-0.2 5 / z m and sub-0.18 # m fields. The connection points or grooves of the elements on the same substrate will be quite shallow. Generally speaking, the formation of an intermediate TiSix layer will require sacrificing part of the Si substrate as the silicon source. The thickness of the available Si substrate is reduced. The consumed Si quality will cause the electronic characteristics of the substrate to deteriorate, and the components constructed according to this will also cause the product to fail or fail to meet the standards. Therefore, this technique requires an alternative method of forming a silicide layer without sacrificing substrate quality or component characteristics. Page 3 ----- K—l · * ------------ Order --------- line IAV. (Please read the precautions on the back before filling this page )

Description of the invention (This method can provide a method for forming a silicide layer in contact with a silicon substrate. The method includes forming a metal containing layer on the Si substrate, and the metal containing layer can be exposed to It is different from the silicon-containing source of the Si substrate. The metal-containing layer will interact with the silicon-containing source to form a silicon-containing metal containing layer that is derived from the silicon-containing source. Single note: _ by The following detailed description and accompanying drawings make the present invention obvious and easy to understand. Among them: FIG. 1 illustrates a device that can be used to implement a specific embodiment of the present invention. A schematic cross-sectional view of a substrate structure belonging to different processing stages according to a specific embodiment of the present invention; FIG. 3 ac is a schematic cross-sectional view of a substrate structure belonging to different processing stages according to a specific embodiment of the present invention; -h is a schematic cross-sectional view illustrating a substrate structure in accordance with a specific embodiment of the present invention and belonging to different processing stages; and FIG. 5 is a process sequence illustrating the silicide formation step in accordance with a specific embodiment of the present invention. In order to facilitate understanding, if possible, the same reference numbers refer to the same elements in the illustrations. Page 4 This paper applies the Chinese National Standard (CNS) A4 Regulations ^^ 297). Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative (please read the notes on the back before filling this page)

478096 V. Description of the invention (Comparison of drawing numbers) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperative, printed 100 processing chamber 102 vacuum pump 106 power supply 114 memory support circuit 118 signal bus 130 gas meter board 170 embedded Heater 190 Semiconductor wafer 200 Substrate 202 Material layer 202H Contact through hole 204 Metal film 205 TiSix layer 207 TiSix layer 302 Silicone layer 402 Chemical absorption layer 406 Ternary compound single layer 410 Chemical absorption layer 420 Silicon-containing environment 130 104 110 116 120 150 172 2001 202B 202S 2041 206 250 305 404 408 415 422 Gas meter panel Gas supply control unit control software nozzle support base Temperature sensor interface Bottom side wall Partial passive metal nitride film substrate structure TiSix layer TiSiJ conductor layer metal plug structure nitrogen environment (please read the precautions on the back before filling this page)

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Detailed description of the invention: The present invention can provide a method for forming a solid contact that has the reliability of a modified element. According to this # _ + Ming, one of which contains silicon (Sl) J Page 5 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 478096 A7

A single layer used as an interposer in a multi-layer metallization structure is formed on a silicon layer or a substrate, but does not consume the silicon of the bottom substrate. This method includes using an alternative Si-based source instead of the bottom silicon-containing layer = a substrate, forming a silicide layer on the substrate, that is, it may contain rhenium or a passive metal. In a specific embodiment, a TiSix layer can be formed on a Si substrate. Compared with the conventional silicide formation technology, the present invention can form the TiSix layer without consuming a large amount of silicon from the Si substrate. The present invention can be used to form the silicide during the fabrication stages of various integrated circuits, for example, when the source and exhaustion parts of the transistor are formed, and the contact surface of the polysilicon gate electrode is used. ---- Π ----%.! (Please read the precautions on the back before filling out this page) Printed wafer processing system printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Figure 1 outlines a wafer processing system 1 〇, and can be used to implement specific embodiments of the present invention. The system 10 includes a processing reaction chamber 100, a gas meter plate 130, a control unit 110, and other hardware components, such as a power supply 106 and a vacuum pump 102. One example of this processing reaction chamber 1000 is a r chemical vapor deposition (CVD) reaction chamber, in which the US Provisional Patent Application No. 〇9 / 2 1 1,998 ', which is commonly designated as described above, is titled "High Temperature Chemical Vapor Deposition Chamber ", which was built on December 14, 1999, is hereby incorporated by reference. The key features of the system 10 are explained in detail below. Reaction chamber 1 0 0 The processing reaction chamber 1 0 0-generally contains the reaction chamber that can be used for the processing. Page 6 This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) Order 478096

V. Description of the invention () Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 100 miles supporting a base such as a semiconductor wafer 190 substrate 150. The base 150 can generally be removed vertically in the reaction chamber by using a displacement mechanism (not shown in the figure). Depending on a particular process, the wafer substrate 190 must be heated to a desired temperature before being processed. In the illustrated reaction chamber 100, the wafer support base 150 is first warmed by an embedded heater 70. For example, the base 150 may be heated in a resistive manner by applying an electronic circuit to the heater element 170 through an AC power supply state 106. Then, the wafer 190 can be heated by the susceptor 15 and can be maintained in a processing temperature range such as 450-75 (rc.) The temperature sensor 1 72 such as a thermocouple is also embedded in the crystal. The base of the circular support 150 is conventionally monitored for the temperature of the base 501. For example, the measured temperature can be used in a feedback loop to control the power supply 106 of the heater element 170 to maintain or Is to control the temperature of the wafer to a desired temperature suitable for a specific processing application. This can be performed through a gas flow controller 130 via a cluster controller (not shown in the figure) and a control unit 110 such as a computer Appropriate airflow control and regulations. The nozzle 120 allows the processing gas from the gas meter plate 130 to be evenly distributed and introduced to the reactor. For example, the control unit 110 includes a central control unit to hold There is a memory for supporting the related control software 1 1 6. The electrical control specialist ii 〇 is responsible for the necessary processing as a wafer, including steps such as transfer, air flow control, temperature control, reaction chamber clearance, etc. Automatic control The two-way communication between the control unit 110 and the system 10 is carried out through a number of signal cables, and is generally designated as a signal bus 丨 18, No. 7 * This paper standard applies to Chinese national standards ( CNS) A4 specification (210 X 297 mm) (Please read the phonetic on the back? Matters before filling out this page) Wei. 丨 line · 478096 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description () The other part is marked in the figure. The vacuum pump 102 is used to remove the processing reaction chamber 100 and maintain the appropriate air flow and pressure in the reaction chamber 100. Through the nozzle i 2 0, the processing gas can be Is introduced into the reaction chamber 100, and the showerhead 120 is located above the wafer support base 150. In some applications, the showerhead 120 is equipped with two separate paths or gas lines that allow two streams of gas to be introduced separately Into the reaction chamber 100 'without mixing first. Details of this "dual-airflow" nozzle 1 20 are disclosed in a commonly designated US provisional patent, entitled "Dual Gas Faceplate for a Showerhead in a Semic" "Onductor Wafer Processing System" in the second article, Xuguang 09 / 098,969, was established on June 16, 1998, and is hereby incorporated as a reference. The nozzle 120 is connected to the gas meter plate 130, and is controlled by mass flow. To (not shown in this figure) 'control and supply various gases used in different stages of the processing sequence. During wafer processing, the exhaust gas supply 104 can also be around the bottom of the base 150 A purging gas, such as an inert gas, is provided so as to minimize the unnecessary deposits formed on the base 150. Fragmentation Figures 2a-c illustrate a specific embodiment of the present invention. In summary, the substrate 200 refers to a working plate on which a thin film processing operation can be performed, and the substrate structure 250 is used to refer to the substrate 200 and many other material layers formed on the substrate 200. In the following, the substrate 200 in Figs. 2a-c refers to a substrate containing a dream layer, or a substrate containing, for example, a polysilicon layer (aggregate gate electrode) or a silicon wafer. Page 8 Γ, -------- ^ --------- (Please read the notes on the back before filling out this page) 478096 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention Explanation () For example, the "this" picture shows a cross-sectional view of a substrate structure 250, which has a metal thin film 204 (the words "film" and "layer" can be used interchangeably with each other), there is really a bed A under the film p 丄, and t Buwan are material layers 202 formed on the silicon substrate 200 first. In this particular description, the τ edge layer 202 can be an insulating layer such as an oxide (such as SiO 2). Traditionally, the 馇 and 赝 layers have traditionally been formed and patterned to provide extensions to the substrate 200. 9ΛΛΤ " On the surface, it is used for contact holes or openings of 202h for 20h. The metal thin film 204 may be a passive metal such as Ti, Ta, or the like. In a condensed example, the metal film 204 can be formed according to, for example, an "electric paddle reinforced electrode M. Gen. enhanced chemical vapor deposition" (pECVD) or "physical plug plating (PVD). ”And other traditional techniques ^ deposition process, and deposited on: structure-... thin film. Generally speaking, the Ti film 204 is deposited within a range of about 25 to 200 angstroms, and preferably within a range. For example, in a monolithic embodiment, the range of 0 to 100 angstroms is about 100 angstroms. However, the thickness varies depending on the application of the 、, // 又, 很, 很, 疋, 疋, 疋, 疋, 亦可, 低于, 亦可, and 丨, and it can also be lower than 很 〇〇angstrom as the component shrinks. The deposited Ti thin film 204 also includes a portion of the substrate that is in contact with a portion of 401, 2_. As in the second example, due to the non-uniform hooking of the deposited Ti film 204, Ti is 909, Λ, ^, φ 1 is any side wall 202S that benefits from contact with the through hole 202H. The present invention is also applied to the uniformity of Shen Ji = film 2.4. Although the Ti film deposition method is not critical to this, the properties of the Ti film 204, such as the appearance of the surface film, are used to determine the processing conditions in subsequent processing steps.

The Ti Λ ΗΜ ΊΠΑ step is used to convert the part 2041 of the Ti boat 204 to TiSi in particular, and the paper standard has been used in Zhongguanjia Standard (CN ^ A4 Specification 撕 χ Tearing-- --- Κ--r, ------------ Order --------- line 丨 ·-(Please read the note on the back? Matters before filling out this page} ^ / 8096 A7

(Please read the precautions on the back before filling this page} In the preferred embodiment, the Ti film 204, including the portion 2041 at the interface 200I, will be exposed to a silicon-containing source or precursor gas Gas environment, such as silicon salt (SiH0 or disilicon salt (shH6), etc.) This silicidation step can generally be performed in a deposition reaction chamber such as Ti or TiN deposition, which contains the flow rate of rare gas About 20 to 3 00 sccm, the total pressure is about 0.5 to 20 Torr, and the temperature is about 500 to 750. (: In the temperature range. Inert gases such as Ar, Ni, He can be separately Or mixed and used together with the precursor-containing gas. For example, for precursor gas SiH ^, its more suitable parameters include a flow rate of less than 3000 seem, preferably about 1000 to about 2000. Between seem, especially 500 seem; its local pressure is about 0 5 to 20 Torr, especially 5 Torr. The inert gas flow rate can be applied to the part containing the fragmented precursor gas according to the desire. Depending on the pressure. Its temperature can be selected in the temperature range of about 500 to 750 ° C, especially 650X: is better. General T 'Although it can generate a faster reaction rate than South temperature, but it may still need a lower temperature due to temperature cost considerations. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the formation of the Ti Six can be single or two The steps are performed. For a temperature higher than 600 ° C, the TiSix layer 205 is formed in a single step by a reaction between the silicon-containing precursor gas and a local 2041 of the Ti thin film 204, as shown in FIG. 2b. In this embodiment, after the silicon-containing precursor gas is introduced into the reaction reaction chamber, a thermal reaction occurs between the Ti thin film 204 and the silicon-containing precursor gas, thereby forming the TiSix. It can be selected Processing parameters in order to enhance the thermal reaction between the local 2041 of the Ti film 204 and the silicon-containing precursor gas, and the 10th most likely reaction between the Ti film 204 and the bottom silicon-containing layer or the substrate 200 is The paper size of this page applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 478096 A7 V. Description of the invention (Minimization. For example, gas containing silicon precursor gas containing a high proportion or local pressure, or Lower substrate temperature, etc., will make the reaction between the butadiene thin film 204 and the silicon-containing gas better. In this way, the butadiene can be contained mainly by the silicon-containing precursor gas with the layer "205". The result is that the thickness of the TiSix layer 205 is generally about 2.5 times that of the Ti layer 204. Of course, the TiSix layer can also be formed on other parts of the thin film 204, such as TiSix layer 2 〇7, located on the upper end of the insulating layer 002. However, the present invention relates to the formation of the silicide layer in contact with a silicon-based material (such as a silicon substrate 200), and the silicon-based material may be Degradation due to silicidation steps using previous techniques. According to the method of the present invention, the total amount of Si introduced into the Ti portion 2041 by the silicon-containing precursor gas at the gadolinium interface 2001 should be sufficient to completely convert the Ti portion 2041 into Tisix. Although the Ti thin film 204 disposed on the insulating layer 202 is completely converted into the TiSix layer 207 as shown in Fig. 2b, it is not necessary to implement the specific embodiment of the present invention. The TiSix layer 205 thus formed will have the desired physical and electronic characteristics to serve as an interposer in a multilayer metallization stack. Therefore, the TiSix layer 205 can be formed accordingly without consuming silicon from the bottom substrate 200. In another embodiment, a plasma processing method may be used to form the intermediary TiSix layer 205. For example, the plasma generated by the silicon-containing precursor gas is additionally matched with one or more inert gases. Various methods can be used, such as radio frequency (RF), microwave, electronic cyclotron resonance (ECR), or remote plasma sources, etc., and then use a variety of commercially available plasma processing reaction chambers to generate privacy. Pulp. In this specific embodiment, the processing temperature may be about 3,000 to page 11 «— — — — -l · —! T — --- · II (Please read the precautions on the back before filling out this page ) · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 478096 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () In the range of 500 ° C, the overall pressure is about 0.5 to 20 Torr. The flow rate of the silicon-containing precursor gas is less than 3000 seem, and is suitably between about 100 and 2000 seem, and preferably 100 sccm. Because the plasma treatment can be performed at a temperature lower than that used for the thermal reaction, the reaction between the Ti film 204 and the substrate 200 can be expected to be suppressed. After the intermediate TiSix layer 205 is formed, the barrier layer, that is, the conductive layer such as a passive metal nitride film 206 can be further deposited, as shown in FIG. 2c. For example, the reaction between titanium tetrachloride (TiCl4) and ammonia (NH3) can be used in the reaction chamber 100 shown in FIG. 1 by the CVD method to form a nitride film (TiN) 206. In the figure, together with tetrachloromethane (TiCU), an inert gas such as helium (He) and nitrogen (N2) is introduced into the reaction chamber 100 through a path (gas path) of the nozzle 120. And through the second path of the shower head 120, NH3 and N2 are introduced into the reaction chamber 100. Here, another gas path and gas supply 104 at the bottom of the reaction chamber 100 will also be provided, and a bottom inert gas exhaust flow (such as Ar) of about 2000 seem will be provided. In general, the reaction can be carried out at a vapor flow rate of titanium tetrachloride TiC 14 of about 5 to 40 seem, plus an inert gas flow rate of about 500 to 5000 seem. The total pressure is between about 3 and 30 Torr, and the base temperature can be greater than 450 ° C (about 600 to 700. (between). Under these processing conditions, the TiN film 206 can be 3.5: The opening at J exhibits at least 95% coverage (the aspect ratio is defined as the ratio of the depth d to the width w of the opening 202H, and TiN is deposited on the opening). Generally speaking If you use other pure metal chopped compounds (such as TaSix, page 12), this paper applies Chinese National Standard (CNS) A4 (210 X 297 mm)----Il · — It— — — —-II ( Please read the note on the back? Matters before filling out this page) Order: • Line. 478096

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs or WSix) as an intermediary silicide layer 205. The barrier layer 206 is preferably a corresponding passive metal nitride, such as a nitride button or nitride. Tungsten. In addition, in the subsequent metal deposition step (not shown) of the 1C fabrication sequence, an additional metal layer such as aluminum or tungsten can be formed, so as to provide a metal connection to the silicon substrate 200 using a well-known technology in the industry. Sexually touching the opening 202H. As before, depending on the processing temperature, the silicide formation operation can be completed in two stages-that is, if the silicon-containing precursor gas is below 600. If the substrate temperature is introduced. This specific embodiment is shown in Sections 3a-3c. Fig. 3a is the same substrate structure as shown in Fig. 2a, wherein the Ti film 204 is formed in a contact through hole 20H after being defined in the insulating layer 202. Part 2041 of the Ti film 204 will contact the silicon substrate 200 at the interface 2000. According to this embodiment, the Si-based layer 30 is then formed on the structure of FIG. 3a by using a chemical vapor deposition method containing a silicon-containing precursor. For example, by using the thermal decomposition of a silicon-containing gas (ie, when siH4 is at about 500 ° C), a uniform Si-based layer 302 can be deposited on the Ti film 204, including the local 2041 and along the The contact edge 2 0 2 S of the through hole 2 02 H is shown in Fig. 3b. The Si substrate layer 302 can be deposited at a SiHU flow rate of less than 3000 sccm, preferably between 100 and 2000 sccm, and most preferably 500 sccm. The local pressure of SiH4 is between 0.5 and 20 Torr, preferably $ t〇r "^. One or more inert gases (such as Ar,% or ^, etc.) can be used to match the SiH4 gas. Application. The thickness of the Si-based layer 30 is generally about twice that of the local portion of the Ti film 2041. For example, the thickness of the Ti film is approximately on page 13. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) · ----- Order --------- Line (Please read the precautions on the back before filling this page)

V. Description of the invention (25 and 200 routes), Ming, ..., People, People, Children Sl quality layer 302-generally is deposited to a thickness of about; lh 〇 and 400 angstroms. This Si-Ti thickness _ Yin degree The ratio of 2: 1 can ensure that ... the local part of the thin film 2041 can be completely converted into a scratch in the subsequent reaction. At first glance, it may be better that the Sl layer 302 is non-crystalline: in order to improve its follow-up The reaction between the local membranes of the thin film, and the reaction between the local membrane and the substrate of the thin film on the same day are minimized. In this way, the parameters of the process for the deposition of the radon-containing substrate can be transformed into non-crystalline μ. For example, which one to use first The mass gas 'temperature is between 3 () () and 6 ° C.' and using the well-known processing parameters of the industry 4 may be suitable for forming the amorphous Si matrix layer 302. For example, the use of ShH6 containing rare earth precursor gas The temperature may be between 200 and 40 ° C. In addition, the Si f layer 3G2 may also be deposited by plasma reaction using appropriate gas containing gas and processing parameters well known in the industry. Once, different plasma sources, such as RF, remote plasma, and so on, can also be used to implement this specific embodiment. As shown in Section 3c No, another subsequent step is performed to start the reaction between the sapphire layer 302 and the Ti film 204 to form the Tisix layer 305. For example, this reaction step can be performed by heating as shown in Figure 3 ^ The substrate shown is structured to at least about 600 ° C. According to the present invention, it is preferred that a portion 2041 of the thin film 204 can be completely converted into a TiSix layer that contacts the interface 2001 of the bottom silicon substrate 200 305. Depending on the specific Ti deposition process and the thickness of the Ti film 204, the other points of the Ti film 204 are those that are located outside the contact through hole 202H and contact the 202 layer. In other words, whether το is completely converted from Ti to TiSix is optional. As mentioned above, this paper on page 14 of this paper rule China National Standard (CNS) A4 specification (210 X 297 public shame)------ --- # ·! (Please read the notes on the back before filling out this page) a ^ T · · Line Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 478096

The invention focuses on a method for forming a silicide layer in contact with this pair of, ah, a continuous layer. In this way, you can adjust the processing parameters of j according to this two-stage program to ensure that the T: film 204 will touch the ^, (please read the precautions on the back before filling this page). The silicon-containing part of the local Shao 2041 can be completely converted. As in the previous month, the Sx quality layer 302 is preferably amorphous, so that the reaction rate between the Si quality layer 302 and the edge film layer 2041 can be as low as that of the Ti film. The reaction between the membrane board # 2041 and the bottom silicon substrate 200. And if the q Λ A ^ ^ substrate 200 contains a polysilicon material (instead of a single crystal) in the second, it is also expected that the partial TU film 2041 can be produced with the si quality layer 30: as desired effect. According to this, the shattered material layer 305 can be formed without consuming the base substrate 2GQ_f, and the substrate 200 is deteriorated. You can continue to use the aforementioned processing method as shown in Figure 2c to perform subsequent conductor layer formation operations (not shown), that is, to use a "Sichuan barrier layer above layer 305." Then perform another metallization step, In order to provide metal connectivity to the silicon substrate 20, the through hole 20H is contacted. As shown in FIG. ^, The Si layer 302 is on the side wall 202S of the contact through hole 202H. It has no effect, but this does not affect the effectiveness of metal connectivity. Figures 4a-h printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics illustrate another specific embodiment of the present invention, where TiSiJ is also a passive metal The silicide (metal silicide) is formed between a chemically-absorbed Ti-containing substance and a Si-containing precursor. In this embodiment, the insulating layer 202 is molded to form the silicon substrate extending to the silicon substrate. After the contact through hole 202H of 200, the Ti-containing substance is chemically absorbed into the substrate structure, including the surface of the insulating layer 202, along the side wall 200S and the bottom 202B of the contact through hole 202H, and The silicon substrate. This can be used on page 15 This paper is applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm) 5. Description of the invention () For example, if the substrate structure is exposed to a substrate containing Tic, the flow rate of Ticl4 is about 50 to 1000 mg / min. Especially between. The mg / min. Is preferable, and the pressure is between about 05 to 20 Torr, and the optimum value of ', y is about 5 Torr. In general, inert gases such as helium, arsenic, Ar, and temples can be used as a load gas to introduce TiCl4 to the place where it can be used as a reaction gas. The temperature of the silicon substrate 20n is generally best maintained at about 45 ° :, but it is still an acceptable range between about 4 °. The 7G () substrate structure is exposed to the Tick airflow for at least a long enough segment, so that the surface of the stone substrate 200 is filled with a saturated Ti-containing monolayer, such as TiCl4 or more generally Ticly substance, where the value of y can be 0 to 4. Such as Tic Bu TiCl2, TiCl3-also known as hypochlorite. If necessary, a reaction gas such as hydrogen (Η.) Can be introduced together with TiC "to the substrate for extraction or interaction with chlorine to enhance absorption of the secondary chlorine Z '. The flow rate of the hydrogen is maintained Between about 500 to 5000 sccm, preferably about 1000 seem. And with a higher substrate temperature, it is more favorable to form the secondary chloride. This can form the thin and Ticly-containing chemical absorption layer 402, and can substantially cover the exposed area of the silicon substrate 2000 (interface 2021), as shown in Figure 4a. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and then using Ar gas and about 3,000seem Flow rate and a pressure of about 5 Torr to carry out the purging step (not shown). The purging process needs to be performed for a long time, for example, about 0 seconds to remove the residual gas phase in the reaction chamber. Contains Ti precursors (such as Ticl4 without chemical absorption on any surface). Other inert gases such as helium or nitrogen are also suitable. Generally speaking, a flow rate of about 1000 to 10,000 seem can be used, and about 2 to 20 Torr The pressure on page 16 is applicable to the national standard of this paper. Standard (CNS) A4 (210 X 297 mm) 478096 V. Description of the invention (according to the different special reaction chamber capacity and conditions, the purge time can be changed to the best. Select the purge gas flow rate High enough to achieve a proper drainage effect in a relatively short time (please read the notes on the back before filling this page). In specific embodiments, the drainage time can be made about 10 seconds. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs after the step A, the substrate structure 45 with the TiCly chemical absorption layer 402 will be exposed to CO containing fragile environment, as shown in Fig. A. The silicon content is 420% Contains a Si-containing precursor such as SiH4, M]%, dichlorosilicate (sici2H2), etc. For example, the flow rate of SiH4 is between about 100 and 5000, preferably 100 seem, The pressure is about 0.05 to 20 Torr, preferably 5 Torr. In addition, one or more inert gases can be used together with the Si-containing precursor in the silicon-containing environment at 42. Temperature 45 (rc, or 疋 is about 400 to 700. (: range, the reaction between TiCly chemical absorption layer 410 and S1H4 occurs A uniform TiSix layer 404 is formed on the insulating layer 202, the contact through hole 202h and the silicon substrate 200, as shown in FIG. 4c. The uniform TiSix layer 404 is generally extremely thin The thickness is limited by the thickness of the absorbing TiClx layer 402. As far as the silicon-containing environment 42 is concerned, the silicon-containing precursor gas flow should be sufficient to fill the surface of the substrate, or at least the TiClx layer 402—consisting of A part of the interface 2001 of the silicon substrate 200 can completely react. At a temperature of 450 ° C, the reaction proceeds at a rate of less than 1 Angstrom (period / cycle) per cycle, such as about 0.4 Angstrom / cycle. By appropriately controlling the processing parameters, such as SiH4 pressure, flow rate, and temperature, the siH4 layer can be formed at the interface 2001 that contacts the silicon substrate 200 without depleting most of the silicon by the substrate 200. Generally speaking, stone-bearing precursors with higher local pressure or flow rate and lower temperature will be more favorable for the paper size on page 17. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (%) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 478096 A7 __ B7 V. Description of the invention () The chemical reaction between the absorbed TiCly and the silicon-containing precursor is the opposite of the reaction with the silicon substrate 200 . In addition, if the excited silicon-containing precursor produced by the low-power plasma is applicable. After the TiSix layer 404 is formed, a purge step (not shown in Figure 4) is performed again to remove any remaining silicon-containing precursors in the reaction chamber. The exhaust gas flow rate and pressure conditions are similar to those used for exhausting Ti-containing precursors. In order to obtain the desired thickness of the synthesized TiSix layer, the steps of chemical absorption of TiCly, exhaustion of reaction chamber, SiH4 gas exposure, and exhaustion of reaction chamber can be repeated as many times as needed. For example, repeating this cycle about 200 to 500 times can form a synthetic TiSix layer suitable for contact applications. Another feature of the invention is that a catalyst can be introduced into the treatment sequence to obtain some desired film properties. For example, after introducing the first precursor TiC1-4 to form an absorbed TiCly layer, a catalyst such as a zinc-containing precursor may be introduced into the reaction chamber. The zinc-containing precursor can be used to remove chlorine (C1) from the absorbed TiCly layer, thus enhancing the formation of hypochlorite. After the catalyst in the reaction chamber is drained off, a second precursor such as SiH4 is introduced and reacted with the secondary chloride to form a silicide layer as previously described. As compared to TiC 丨 4, the reaction between SiH4 and hypochlorite will be faster, and the use of a zinc-containing catalyst allows the temperature of the substrate used to form the T i S i X layer does not need to be too high, which is more conducive to SiH4 The response is the opposite of that of the silicon substrate 200. Another feature of the present invention is that other papers such as T i and S i Page 18 This paper size is applicable to China National Fresh (CNS) A4 (210 X 297 mm 1 '" ------ ----------- Order --------- line " ^ ΙΙΓ (Please read the note on the back? Matters before filling out this page) 478096 A7 B7 V. Description of the invention () (Please read the note on the back? Matters before filling out this page) The object 'in addition to TiSix can also be used to form the silicide contact. For example, you can add nitrogen-containing precursors to the above processing sequence, A ternary compound containing Ti, Si, and nitrogen (N) is formed. In a specific embodiment, the 'Ti-containing substance can be absorbed onto the substrate surface as shown in Figure 4a, and then the reaction chamber is drained, and then The second precursor, the silicon-containing precursor, is introduced into the reaction chamber, similar to Figure 4b. The reaction between the absorbed Ti-containing layer and the silicon-containing material will form the TiSix layer 404, or More broadly, it is similar to the reaction product layer of Fig. 4C. After the reaction chamber is drained, a third precursor such as a nitrogen-containing substance is introduced into the reaction chamber. Fig. 4d shows The TiSix layer 404 is exposed to the nitrogen-containing environment 422, in addition to the nitrogen-containing substance or containing other inert gases. As shown in FIG. 4e, the distance between the TiSix layer 404 and the nitrogen-containing substance is The reaction will form a single layer 406 containing a ternary compound such as TiSixNz. Although each element of the binary compound can be introduced by an individual precursor, in some cases a single precursor can still be used to provide more than one desired compound Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Generally speaking, “different precursors can be introduced in different orders in this processing sequence. Conventionally, the precursors are introduced into the processing or reaction sequence order” system Taking into account factors including absorption characteristics or precursor reaction rates or intermediates formed during the reaction sequence, it is selected to optimize the desired reaction output. After forming the TiSix layer 404, or more Broadly speaking, after the metal silicide layer 406 (the layer may contain non-binary compounds, as shown in Figure 4e), subsequent processing steps may be performed to complete the multilayer metallization stack For example, on page 19, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 478096 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Figure 4f is displayed on the metal A conductive layer 408 is formed on the silicide layer 406. According to various specific applications, the conductive layer 408 may be a nitride layer, such as TiN or other pure metal nitride with suitable barrier properties. For example, it may be thermal or Plasma CVD uses the reaction between titanium tetrachloride (TiCl4) and ammonia (NH3) and uses well-known processing parameters in the industry to form the TiN layer 408. In addition, it can also be borrowed from appropriate precursors. The conductive layer 408 is formed similarly to the processing steps disclosed in FIGS. 4a-4e. For example, if the conductive layer 408 is TiN, TiClx can be absorbed or chemically absorbed into the metal debris layer 406 by providing TiCI4 according to processing parameters similar to those described above. When too much TiCl4 is removed from the reaction chamber, TiClx, which has been absorbed or chemically absorbed, will react with NH3, which is preferably at a flow rate of about 100 to 3000 seem, especially 500 sccm, and is introduced into The reaction chamber. This will form a thin TiN layer inside the opening 2 0 2 Η with excellent step coverage. If required, additional cycles (absorption and reaction 'plus drainage) can be performed to provide a thicker synthetic TiN layer. In addition, the TiN layer 408 can also be generated by a combination of absorption reaction modes and cVD TiN. In another specific embodiment, the conductor layer 408 may also be, for example, a circuit containing a metal nitride such as a passive metal and a metal nitride such as Ti, TiN, hafnium (Ta), hafnium nitride (TaN), and the like. / Barrier layer combination layer. Next, as shown in FIG. 4g, a metal layer 41 is formed on the TiN layer 408. The metal | 410 may include, for example, chicken gizzards or maggots. For example, with the well-known processing parameters in the industry, let the CVD be the 20th page of the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -l · --f ------ ------ ^ --------- line i ^ w. (Please read the precautions on the back before filling this page) 478096 A7

A tungsten gold layer 410 was generated between the rhenium hexafluoride (WFd * _a, ττ, MWF6) and the milk lice (乳 2) <. In the subsequent steps, a part of the metal layer 410 located on the outside of the contact through hole 2 0 2 备 is prepared from the sparse lice compound layer 408 and the metal nitride layer 406. Preparing the micro maple (CMP) plane technology and removing it 'produces a metal plug structure 415 as shown in FIG. 4h. It should be noted that the specific metallized snails or sequences described in this consideration are for illustrative purposes only. Regarding the formation of this dream, it is also possible to know how to apply other processing sequences that use different material layers or processing techniques in accordance with the specific examples of the present invention. FIG. 5 illustrates a processing sequence 500 that incorporates various steps of the present invention to form a non-substrate degraded intervening tungsten silicide layer. These processing steps can be performed in a typical cvd or PVD reaction chamber, which is similar to a Ti or TiN deposition operation. As shown in the figure, step 502 provides a silicon-containing substrate (also referred to as a silicon-based substrate) in the reaction chamber. According to a specific 1C production stage, the silicon-containing substrate may or may not already have a material layer. The material layer may be, for example, an oxide layer having a contact through hole extending to the interface of the silicon-based substrate (in this way, a part of the rare-based substrate may be exposed). The object of the present invention is to contact a silicide layer forming operation of the silicon-containing substrate. At step 504, an intervening silicide layer, such as a metal silicide layer, is formed and contacts the silicon-containing substrate. According to a specific embodiment of the present invention, the various kinds of methods and different precursors can be used to achieve the formation of the crushed material. A method follows step 506, where a conductor layer is first formed on the silicon-containing substrate. For example, the conductor layer may be a metal layer formed by containing a suitable metal precursor such as Ti or other passive metals. At step 508, a silicon-containing source or precursor is provided to conform to the Chinese paper standard (CNS) A4 (210 x 297 mm) on page 21 of the paper deposited from step 506. ----- rut- ------ C Please read the notes on the back before filling this page)

J ^ T-丨 Line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 478096 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () The metal reacts to form an intermediary fragmentation layer. The intermediary fragmentation layer may be, for example, a TiSix layer formed by a technique selected from one of the following: exposing the Ti layer to a full Si environment (ie, SiH4 or Si2H6); or a deposited Ti layer and a The solids between the Si layers (amorphous or polysilicon) deposited by silicon-containing precursors such as SiH4 or Si2H6 act on solids. In addition, other suitable precursors may be used to form the intervening metal chopper layer such as lithium silicide, tungsten silicide, and the like. In addition, as shown in step 5 10, the intermediate metal dream layer at step 504 can be formed by a reaction (such as thermal or plasma strengthening) between a suitable precursor of the metal halide and the silicon-containing gas. . Taking the TiSix layer as an example, precursors such as TiCU and SiH4 can be used. According to a specific embodiment of the present invention, the first precursor is absorbed as a thin thin layer or a single layer on a silicon-containing substrate. Then, the absorbed first layer is exposed to a second precursor to form a silicide layer. Moreover, you can choose whether to form the silicide layer, adjust it to introduce a catalyst to promote the desired reaction, or add a second precursor for further processing (not shown in Figure 5). . According to a specific embodiment of the present invention, the selection conditions of various silicide formation procedures are based on the metal silicide layer being formed mainly by a reaction from a silicon-containing source or a precursor different from the silicon-containing substrate. In this way, the metal silicide layer is composed of silicon mainly from a silicon-containing source, and the consumption of the silicon in the bottom substrate can be minimal or negligible. -At step 512, a conductive layer may be formed on the intermetallic silicide layer formed at step 504 by providing an appropriate precursor to the substrate in the reaction chamber. The conductor layer can be, for example, metal nitride J (such as Ding ... Page 22 This paper size applies Chinese National Standard (CNS) A4 specifications (21 × 297 mm) (please read the precautions on the back before filling this page) Order · Line · 478096 A7 ------_ B7__ 5. Description of the invention () To be used as a barrier layer, or a line / barrier layer combination in a metallized stack. After that, additional processing steps can be added. (Illustrated) to deposit other appropriate conductor layers (such as tungsten or aluminum) on the conductor barrier layer, so that semiconductor components can form subsequent conductor paths or connectivity. In this way, by providing external In the specific embodiment of the present invention, a silicide layer can be formed on the silicon-containing substrate by contacting the silicon-containing substrate, thereby avoiding unnecessary material loss of the substrate-containing substrate. In this way, the present invention can provide a method for forming a semiconductor element. Silicide method with improved reliability and performance characteristics. Although this article borrows several better specific embodiments and the teachings of this invention to elaborate, for those who are familiar with this technology, this Make a lot of specific embodiments that are still within the demonstration of the teaching. ----- Bu —Γ ------------ Order --------- line (please first Read the notes on the back and fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, page 23 This paper size applies to China National Standard (CNS) A4 (210 X 297)

Claims (1)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 478096 A8 B8 C8 D8 6. Scope of Patent Application 1. A method for forming a silicide layer contacting a silicon substrate, the method includes the following steps: (a) contacting the A silicon-containing substrate to form a metal-containing layer; (b) exposing the metal-containing layer to a fragment-containing source different from the broken substrate; and (c) formed by the interaction between the metal-containing layer and the silicon-containing source A metal silicide layer; the metal silicide layer is mainly formed by the silicon from the silicon-containing source. 2. The method according to item 1 of the scope of patent application, wherein the metal-containing layer in step (a) above is an absorbed layer formed by exposing the silicon substrate to a metal-containing precursor. 3. The method as described in item 2 of the patent application scope, further comprising: (al) performing the steps (a) and (b) in a reaction chamber; and (a2) in steps (a) and ( b) The reaction chamber is drained in between. 4- The method according to item 3 of the scope of patent application, wherein the aforementioned metal-containing precursor is TiCl4. 5. The method according to item 3 of the scope of patent application, wherein the silicon-containing source in step (b) above is selected from the group consisting of a silicon salt, a disilicone salt and a dichlorosilicone salt. Page 24 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) ϋ ϋ ϋ I ϋ ϋ One-port, ϋ ϋ ϋ I ϋ ϋ II ϋ ϋ I ϋ — ϋ ϋ I ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ I ϋ I ϋ I ϋ I ϋ I 478096 A8 B8 C8 D8 ________ 夂 、 Applicable patent scope 6. The method described in item 3 of the patent scope, It also includes the following steps Λ: (d) draining the reaction chamber after step (C); (e) exposing the previously formed metal silicide layer to the reaction-containing metal precursor, thereby constituting Another absorbed metal-containing layer; and (f) draining the reaction chamber after step (e); (g) by exposing the other absorbed metal-containing layer to a fragile environment, The metal silicide layer is formed on the metal silicide layer. (h) Repeat steps (d) to (g) for additional periods' to form a metal silicide layer having a desired total thickness. 7. The method according to item 3 of the scope of patent application, further comprising the following steps: (a2) after step (a1), exposing the metal-containing layer to a metal silicide containing step (c) ) Catalyst precursor; and (a3) drain the reaction chamber between steps (a2) and (b). 8. The method according to item 3 of the scope of patent application, further comprising the following steps: (d) draining the reaction chamber after step (e); (e) exposing the metal silicide layer of step (c) In a nitrogen-containing environment, a thin layer containing a ternary metal silicide is formed. Page 25 This paper size applies Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the precautions on the back before filling out this page). Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs --- ------ ^ -----------------------. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 478096 AS B8 C8 _ D8 VI. Application Patent scope 9. The method as described in item 4 of the scope of patent application, wherein the above-mentioned absorbed layer is formed at a flow rate of T i C14 of about 50 to 100 mg / min. 10. The method according to item 4 of the scope, wherein the above-mentioned step (0 is performed at a flow rate of the silicon-containing source of less than about 5000 scem. 1 1. The method according to item 4 of the scope of patent application, wherein, Step (c) is a partial waste force performed at the source with a fragmentation of about 0.5 to 20.0. 12. The method according to item 4 of the scope of patent application, wherein the above step (0 is performed The temperature is between about 400 and 700 ° C. 1 3 · The method described in the second patent application scope, further comprising the following steps: (d) Silicon silicide A conductive layer is formed on the layer, wherein the conductive series is a metal nitride. 14. The method as described in item 丨 of the scope of patent application, wherein the above-mentioned metal-containing layer is a metal layer. The method according to item 14, wherein the above-mentioned metal layer is composed of a passive metal selected from the group consisting of 姮, thorium and tungsten. ^ 〇 ------------- φίίί — Order --------- Line ------------------------ (Please read the notes on the back before filling this page) Page 26 4/8096 The application is printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For example, please refer to the method described in item 14 of the patent scope, where the above-mentioned gems are selected from the group consisting of silicon salts, disilicon salts, and dichlorosilicon salts. In the group, the method described in Item 14 of the declared patent fan park, wherein the aforementioned silicon-containing source is an amorphous silicon layer formed on the metal-containing layer. 18. The method as described in item 17 of the scope of the patent application, wherein the non-crystalline silicon layer described above is formed by thermal decomposition of a silicon salt (SiH4). 19 .: A processor can read the storage medium, where the medium contains-processing the Γ L item fetching code, and can control the processing of the reaction chamber when the code is executed-a processing chamber for contacting the broken substrate And forming a hardened material layer < method, the method includes the following steps: U) contacting the silicon substrate to form a metal-containing layer; (b) exposing the metal-containing layer to a source different from the silicon substrate And (c) forming a metal lithosphere layer through the interaction between the metal-containing layer and the silicon-containing source, wherein the metal fragmentation layer is mainly formed by the silicon from the silicon-containing source. Port 20. The processor-readable storage medium as described in item 19 of the scope of the patent application, wherein the metal-containing layer in step (a) above is to expose the silicon substrate to a metal-containing precursor The formed absorbed layer. Page 27 This paper size applies China National Standard (CNS) A4 specification (210 X 297 public love) ---- ItII Bu ----- Φ ---- l · --- Order ----- ---- Line I, (Please read the precautions on the back before filling in this page) 478096 A8 B8 C8 D8 6. Application for patent scope 2 1. The processor can read and store as described in item 19 of the scope of patent application In the media, the above-mentioned metal-containing layer is selected from the group consisting of titanium, niu, and tungsten, and the above-mentioned silicon-containing source is selected from the group consisting of silicon salt, disilicon salt, and dichlorosilicon salt. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, page 28 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) n 1 ^ 1 III— ^^ 1 ni ^ i in 1 ^ 1 ^^ 1 i ^ i I ϋ i ^^ 1 Ha i ^ i in _