TW441001B - Method for reducing chlorine content in titanium nitride layer - Google Patents

Abstract

A method for forming a titanium nitride layer on a semiconductor substrate comprises using a chemical vapor phase deposition to form a titanium nitride layer on a semiconductor substrate; introducing a hydrogen-containing atom group to react with the chlorine impurity in the titanium nitride layer to form a hydrogen chloride gas for thereby reducing the content of chlorine impurity in the titanium nitride layer, in which the hydrogen-containing atom group is formed by using a remote plasma system (RPS) to dissociate a hydrogen-containing gas. Furthermore, the chlorine contained in the titanium nitride layer will diffuse to the surface of the titanium nitride layer and combine with the hydrogen-containing atom group.

Description

4 4 1 0 0 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Field of the invention: The present invention and a method for chemically vapor deposition (CVD) are used to form a titanium nitride layer It is related to the semiconductor manufacturing process. In particular, it is a method for reducing the gas content of the titanium nitride layer formed by using a remote plasma system (RPS) in the process of depositing the titanium nitride layer. Background of the Invention: With the continuous progress and development of the semiconductor industry, in the related manufacturing design of ultra large integrated circuits (ULSI), in order to meet the design trend of high-density wafers, the size of various components has been continuously reduced. In addition, due to the ever-decreasing component sizes, unprecedented difficulties have been encountered when carrying out related semiconductor processes. For example, for capacitors in common DRAM structures, due to the reduction in size, the thickness and dimensions of each film layer are also greatly reduced. In this way, how to effectively reduce the resistance of the upper and lower electrode plates, increase their ability to store charges, and improve the properties of the interface between the electrode plate and other film layers, has also become a subject that the industry must improve ^ General and S ' Because Chin metal easily cross-diffuses with Shi Xi substrate, it forms a compound with a low resistivity (such as TiSi2), and can form a good ohmic contact between its interfaces. Therefore, in the semiconductor-related process, Chin metal The paper size is applicable to the national standard (CNS) A4 specification (210x297 mm) I — I — — 111 — — — — ^. — — 1 ---- Order -------- I {Please first (Notes on the back of the occasional reading, please fill out this page again) 0 1 A7 B7 V. Description of the invention () It is widely used. The associated thin film titanium nitride (TiN) formed from titanium metal is also widely used in semiconductor metal manufacturing processes. Among them, aluminum metal, which is a metal connection structure in semiconductor manufacturing processes, is often used in conjunction with The contact surface of the silicon substrate 'spikes'. Therefore, the above-mentioned titanium nitride layer is often used as a barrier material between a metal and a hard substrate. Furthermore, the titanium nitride layer formed by chemical vapor deposition (CVD) can provide good coverage characteristics and stability. 'As the size of the semiconductor device shrinks, the surface shape is extremely complicated. As for the semiconducting hafnium substrate, the process of forming a titanium nitride layer using the CVD method has received more attention. The typical CVD titanium nitride layer manufacturing process includes the use of titanium tetrachloride (TiCl4), ammonia (NH3) and hydrogen (H2) to form the required titanium nitride film layer. The relevant chemical formulas are as follows: 6TiCl4 + 8NH3 ^ 6TiN + 24HC1 + N2 2TiCl4 + 2NH3 + H2 ^ 2TiN + 8HC1 2TiCl4 + N2 + 4H2 ^ 2TiN + 8HC1 Among them, it can be at a temperature of about 400 to 700. The process of titanium gasification and ammonia gas deposition by chemical vapor deposition (CVD), or at a temperature greater than about 7001 :, and titanium gas, hydrogen gas and hydrogen gas are passed in. In the environment, a hafnium nitride layer is deposited. It should be noted that when the chemical vapor deposition method is performed, the titanium nitride film layer formed usually has 1.8 to 2.5%. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm). ------------ "Clothing ------- Order --------- line '" (Please read the precautions on the back before filling this page) Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau, 441001 A7 V. Invention Description). In addition, "the resistance of the titanium nitride layer is reduced due to the presence of gas impurities", thereby reducing the performance of the titanium nitride layer. In addition, when a vaporized titanium layer is used as an electrode of a capacitor, excessive gas impurities will also cause the leakage current of the capacitor to be too serious. In general, the titanium nitride film layer formed at a lower temperature tends to have a better uniformity, that is, its step coverage characteristics are better. However, it should be noted that at a lower temperature, the titanium nitride layer formed does have a relatively large amount of gas impurities, which will also cause the titanium nitride resistance to increase. In the patent case of Taiwan Patent Publication No. 2 4 1 31, a square enamel for reducing the gas content in the titanium nitride layer is disclosed. Among them, the wafer 14 is first placed on the operation platform 12 in the reaction chamber 10. Then, by using a low-pressure chemical vapor deposition (LPCVD) method, a reaction gas including titanium tetragas and ammonia gas is input from an entrance port μ on the reaction chamber 10. The temperature of the reaction chamber 10 is maintained between 65 ° and 680 ° C, and the pressure is controlled between 115 and 300 mTorr. Thus, a titanium nitride film layer 15 can be formed on the wafer 14. It should be noted that after the formation of the titanium nitride film layer I 5, the supply of titanium tetragaside was stopped, but the input of N H 3 was still maintained. In this way, the input NH; will produce a chemical reaction with the gas in the titanium nitride film layer 15 to generate HCI. Then, use the air extractor to extract the HC1 gas generated from the reaction chamber 10 in order to effectively reduce the gas content in the titanium nitride film layer 15 (Please read the precautions on the back side before filling in this buy)

Packing -------- Order --------- I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, but because of the above use of NH3 and impurities in the titanium nitride layer 15 C1 4 This paper size is applicable + National National Standard (CNS) A4 specification (210x 297 mm) Δ d1 0 0 1 Α7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on consumer cooperation Du B7_V. Description of the invention (If) to reduce the titanium nitride layer 15 The method of C1 content is to make NH3 and C1 chemically react in a high temperature environment of about 65 0 ° C. This is because it often takes more time and a larger thermal budget (thermal b u d g e t). In this way, since the entire wafer 14 is maintained in a high temperature environment for a long period of time, the performance of these semiconductor elements will be reduced for other semiconductor elements already formed above the wafer 14. In addition, the cost (c0st) of the entire related process will be greatly increased. OBJECTS AND SUMMARY OF THE INVENTION The object of the present invention is a method for reducing the content of gas impurities in the titanium nitride layer formed to reduce the resistance 値 of the titanium nitride layer and improve its conductive properties. Still another object of the present invention is to use a remote plasma system (RPS) to produce hydrogen-containing atomic groups, so as to combine with the gas in the titanium nitride layer to synthesize hydrogen gas, thereby achieving a method for reducing chlorine impurities in the titanium nitride layer. . Another object of the present invention is a method for manufacturing a capacitor using a titanium nitride layer as a top electrode of a capacitor. The present invention provides a method for forming a titanium nitride layer on a semiconductor substrate. Among them, first use a chemical vapor deposition method to form a titanium nitride layer in a semi ------- —ill II »i I 1 I f II ---- JI I-- (Please read the precautions on the back before filling (This page) * This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 44100 1

V. Description of the invention () Printed on the conductor substrate by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Then, a plasma process is performed on the hydrogen-containing gas to produce a dissociated argon-containing atomic radical. And pass into the reaction chamber containing hydrogen atoms trapped in the semiconductor substrate, it must be noted that the semiconductor substrate is heated to a temperature of about 250 to 6 50 01. This is so that the hydrogen-containing atoms can react with the gas in the titanium dioxide layer and generate a hydrogenated gas. The gas in the gas layer is diffused toward the surface of the titanium nitride layer and combined with hydrogen-containing atom groups to reduce the gas content in the gasified titanium layer. In addition, the present invention also provides a related process for forming a capacitor with a top electrode and a nitride drum layer. A dielectric layer is first formed on the semiconductor substrate. Next, the dielectric layer is etched to form contact holes in the dielectric layer, and the upper surface of the semiconductor substrate is exposed. A conductive plug is formed in the contact hole to connect other components on the semiconductor substrate. Then, a conductive layer is formed on the upper surface of the dielectric layer and the conductive plug to serve as a bottom electrode of the capacitor, and is electrically connected to the conductive plug. A capacitor dielectric layer is formed on the surface of the conductive layer. Subsequently, a titanium nitride layer is formed on the surface of the capacitor dielectric layer to serve as the top electrode of the capacitor. The titanium nitride layer is formed using a chemical vapor deposition (CVD) method and is passed through a hydrogen-containing atomic group to communicate with Nitrogen gas impurities in the Chin layer are formed to form hydrogenated hydrogen gas, and the content of gas impurities in the titanium argon layer is reduced. The atomic hydrogen containing hydrogen is a long-range plasma system (ememte plasma system; RPS). The gas formed by dissociating the hydrogen-containing gas and located in the titanium nitride layer will diffuse to the surface of the titanium nitride layer and combine with the hydrogen-containing atomic group. This paper size applies to Chinese standards < CNS) A4 regulations < 210 X 297 public love) ί Please read the precautions on the back before filling in this page) Installation · ---- I--Order, --- ----- Line 4 d 1 〇〇1 A7 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B7_V. Description of the invention () Schematic description of the drawing: With the following detailed description in conjunction with the attached diagram, The above content and many advantages of this invention can be easily understood, among which: The first figure is a cross-sectional view of a low-pressure chemical vapor deposition device, showing that according to the conventional technology, a low-pressure chemical vapor deposition device is used to form a titanium nitride layer on a semiconductor Steps on the substrate; The second figure is a cross-sectional view of a semiconductor wafer, showing the steps for forming a titanium nitride layer on a semiconductor substrate according to the present invention; the third figure is a cross-sectional view of a remote plasma system, showing the method according to the present invention The step of using a remote plasma source device to reduce the gas content in the titanium nitride layer; The fourth figure is a cross-sectional view of a semiconductor wafer, which shows the method of performing a capacitor structure on a semiconductor substrate using the method provided by the present invention. Steps * The fifth picture is half A cross-sectional view of a conductor wafer shows the steps for defining the bottom electrode of a capacitor on a semiconductor substrate; and FIG. 6 is a cross-sectional view of a semiconductor wafer showing the step of using a titanium nitride film as the top electrode of a capacitor on a semiconductor substrate. Detailed description of the invention The invention discloses a method for using a long distance after the titanium nitride layer is formed ---- It-I ---------- Order ---- I ---- (Please Please read the precautions on the back before filling this page.) This paper size is applicable to Chinese National Standard (CNS) A4 specifications (2〗 0 X 297 mm) A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A plasma system (remote plasma system; RPS) performs a plasma process on a gas containing gas to generate a hydrogen-containing atomic group. And by passing in this gas-containing atomic group, it will chemically react with the gas in the nitride layer to form a hydrogenated gas and remove it. As a result, the gas content in the titanium nitride layer can be greatly reduced, so that the nitrided nitride produced has a lower resistance, and better conductive characteristics. A detailed description of the present invention is as follows. First, please refer to the second circle, which is shown as an example provided by the present invention to reduce the gas content in the formed titanium nitride film layer. Among them, first, a single crystal silicon having a crystal orientation of < 100 > is provided as a semiconductor substrate 28. Generally, other types of semiconductor materials such as arsenide, germanium, or silicon on insulator (SOI) on the insulating layer can be used as the semiconductor substrate. In addition, since the characteristics of the surface of the semiconductor substrate do not cause a special influence to the present invention, < 110 > * < Ul > can be selected depending on its crystal orientation. Then, as described above, a titanium nitride layer 30 may be deposited on the semiconductor substrate 28 by using a chemical vapor deposition (CVD) method. In general, the required titanium nitride layer 30 can be formed by using titanium tetrachloride (TiCI,), nitrogen (ND and hydrogen (HJ as reaction gases) in the manufacturing process. In a preferred embodiment, Titanium tetragas and ammonia gas can be passed in at a temperature of about 4,000 to 700 to form a titanium nitride layer 30. In addition, titanium tetragas and gas can be passed in an environment with a temperature greater than 700 ° C. And < Please read the precautions on the back before filling out this page > 'i II f III · II — — — — — — This paper size is applicable to National Standards (CNS) A4 (210 X 297 mm). Άά \ 0 0 1 Α7 Β7 Consumption cooperation between employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed 5. Description of the invention (hydrogen to deposit a titanium nitride layer 30. Please refer to the third figure, after the titanium nitride layer 30 is formed, the The semiconductor substrate 28 is placed in the remote plasma system 20 to perform the procedure of reducing the chlorine content in the titanium nitride layer 30. Generally, hydrogen such as hydrogen (H2), helium can be input through the inlet 32 (NH3) and other hydrogen-containing gas, enter the first reaction chamber 22 of the remote plasma system 20. Then, by carrying out the hydrogen-containing gas Slurrying procedure, to produce a dissociated hydrogen atoms of the storm (Radical). Wherein, in a first reaction chamber 22, using a power of about 2,000 to 4000 Watt microwave 34, a hydrogen-containing gas plasma dissociation procedure.

Then, the dissociated argon-containing atomic group can be introduced into the second reaction chamber 24 through the conduit 33. At the same time, the above-mentioned semiconductor substrate 28 'having the titanium nitride film layer 30 is placed on the operation platform 26 in the first reaction chamber 24. And ', the temperature of the second reaction chamber 24 is controlled to about 250 to 65 ° C. Among them, in a preferred embodiment, the 'operation platform 26 can be used as a heating plate for heating the semiconductor substrate 28' or a semiconductor light source (Ump) can also be used to heat the semiconductor substrate 28. In this way, the introduced hydrogen-containing atomic group can react with the gas located in the titanium vaporized layer 30 to generate vaporized argon (HC 丨) gas. Therefore, the gas in the titanium nitride layer 30 diffuses toward the surface of the titanium nitride layer 30 and combines with the hydrogen-containing atoms introduced into the second reaction chamber 24. This will effectively reduce the gas content in the nitriding layer 30. ―In general, the poorly generated hydrogenated gas can be added from the second reaction chamber 24 through the suction line 25. This paper size is applicable _ National Standard (CNS) A4 specification (210 X 297 mm) I ----------- install --- I I--1 order -------- * line (please read the precautions on the back before filling this page) 4 5 4-Ministry of Economic Affairs Intellectual Property Bureau Employee Consumption Cooperation Du Printed 0 0 A7 B7 Invention Description (Note that Λ (please read the precautions on the back before filling this page) In the above example, '疋 Use chemical gas cypress = process First deposit the hafnium nitride layer 30, and then place it in a remote electrical system (RPS) to perform the relevant procedures to reduce the gas content of the hafnium nitride 3Q. However, in the real array: pole strain +, ^ In I operation, you can also order in the same reaction chamber,

Reduce the exhaustion in the titanium nitride layer 30. "A B gas 3 measurement process. That is, according to the present invention, a method for forming a titanium argon with a thorium yang ancient resistance 民, low gas volume, can use a synchronization program according to the system equipment used. ~ 心 procedure ) Or non-synchronous procedures (ex shu prOcedure) to complete. That is, in the case of synchronous procedures, you can order the deposition of titanium nitride layer 'in the same reaction chamber, and after the deposition procedure is completed, then Perform a step of trapping hydrogen atoms to form a hydrogenated gas, and reduce the gas content in the titanium nitride layer = then 'please refer to the fourth step, the figure shows the nitriding produced by the method of the present invention “The film layer is applied to the embodiment of the capacitor of the Dram structure. Among them,“ Because of the titanium nitride film layer produced by the method of the present invention, it has a lower gas content ”because of its lower resistance. Also, in the following, In the embodiment, 'is used as an electrode plate of a capacitor. In a preferred embodiment, a semiconductor substrate 42 is provided, and various types of components are formed in advance on the upper surface of the semiconductor substrate 42. A silicon oxide layer 44 can be formed on the semi-conductive substrate 42 as an insulating layer. A silicon nitride paper can be used in accordance with the national standard (CNS) A4 specification (21 × X 297). (Centimeter) ο ο ill

7 7 A P -------------- V. Description of the invention () Layer 4 6 is on the silicon oxide layer 44 'as an etching stop layer. Among them, in a preferred embodiment, the 'silicon oxide layer 44 is a silicon dioxide having a thickness of about 3000-8000 angstroms formed by using orthosilicate. In addition, the formed nitride nitride layer 4 6 ′ has a thickness of about 500 to 15 Angstroms. Next, the silicon oxide layer 44 and the silicon nitride layer 46 are etched to form a contact hole on the substrate 42. Generally, a region can be defined as a contact hole by first forming a photoresist layer on the silicon nitride layer 46. As for the engraving process used, plasma etching technology can be used to perform it. You can choose ccl2F2, CHF3 / CF4, CHF3 / 02, ch'hf :, CF4 / 〇2 as the etchant for removing silicon dioxide, and select CF4 / as the etchant for removing silicon argon. H2, CHF 3 or CH 3 CHF 2. After forming the contact hole on the semiconductor substrate 42, a conductive plug 48 may be formed in the contact hole β. In a preferred embodiment, a doped polycrystalline wafer (not shown) may be deposited on the nitride wafer 46 first. The top surface is filled in the contact hole, and then the etch-back process is performed on the doped polycrystalline silicon layer until the silicon nitride layer 46 is reached. In this way, a desired conductive plug 48 can be formed in the contact hole. Generally speaking, the material of the conductive plug can be doped polysilicon, in-Situ doped silicon, chain, ditch, tungsten, platinum, or thorium. As for the step of polycrystalline crushing to form the conductive plug 48, the etchant used to etch the polycrystalline silicon is SiCl4 / Cl2, BCI3 / Cl2, HBr / CI2 / 〇2, HBr / 〇2, Br2 / SF6 This paper size applies the national standard (CNS) A4 specification (210 X 297 mm) —1 I 11 I 11 II— 1 · I t—. T Please read the notice on the back c before you fill out this K > Order * '• Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () or SF 6 〇 Please refer to the fifth figure, after forming the conductive plug 48', then define one as the bottom electrode of the capacitor The conductive layer 50 is on the upper surface of the argon fragmentation layer 46 and the conductive plug 48. Among them, the material of the conductive layer 50 can be selected from doped polysiiicon, in-situ doped polysilicon, or metal such as copper, tungsten, platinum, or demon. Next, a semi-spherical silicon grain (Hemi_SPherical Grain; HSG) 52 can be selectively formed on the surface of the conductive layer 50. In this way, the area of the bottom electrode of the capacitor can be effectively increased. Generally speaking, it can be formed by first forming a silicon seed (nuclei) on the surface of the conductive layer 50. For example, it can be formed by using a gas containing silicon such as 3 丨 114 or Si2H6. The process temperature is about 500 eC to 600. • Between 0 and about 10_3 to 10_5 Torr. Then in a highly hollow environment, a thermal tempering process is performed to form hemispherical silicon grains 52. The process temperature is about 500 * C to 600-C, and the pressure is about 10-7 to 100.9 Torr. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Then, as shown in the sixth figure, 'the conductive layer is formed as the bottom electrode of the capacitor 50 and the hemispherical silicon grain 5 2 after. A thin capacitor dielectric layer 54 may be formed along the surface of the bottom electrode structure (50, 52). In a preferred embodiment, the capacitor dielectric layer 54 can be formed by using a thin film of high dielectric mass such as "In addition, other high dielectric mass materials such as BST, PZt, PLZT can also be used as the above-mentioned capacitive dielectric layer 54. It should be noted that in order to avoid the deposition of high dielectric Ta2Os thin films, the oxygen and the paper size applied to the Chinese National Standard (CNS) A4 specification (210 X 297 ^^ 441 00 1 A7 87 V. Description of the invention () High temperature environment causes hemispherical silicon grains (HSG) 5 2 The silicon dioxide film is formed on the surface. After defining the hemispherical silicon grains (HSG) 52, a silicon nitride is formed first. The film layer is covered on the hemispherical silicon die 52, and then the capacitor dielectric layer 54 is produced. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). A titanium nitride layer 56 is formed on the surface of the dielectric layer 54 to be used as a top electrode. As mentioned above, by using a chemical vapor deposition (CVD) method, titanium tetrafluoride and ammonia gas can be passed in. Under the environment of hydrogen and hydrogen, a titanium nitride layer 56 is first formed on the capacitor dielectric layer 54. Then, a remote plasma system (RPS) is used to perform a gas-reducing procedure on the titanium nitride layer 56. Similarly, By passing in a plasma substance containing hydrogen radicals 'And maintaining the semiconductor substrate 42 in an environment with a temperature of 250 to 650 * C' will effectively promote the gas in the titanium nitride layer 56 to generate argon atom groups on the surface of the titanium nitride layer 56 through diffusion. It reacts and forms hydrogen gas gas. In this way, the gas content in the titanium nitride layer 56 can be effectively reduced. Moreover, due to the decrease in the gas content, the titanium nitride layer 56 formed has a lower content. The resistance is 値, and 敫 can be used as the top electrode of the capacitor. Generally speaking, when the temperature of the semiconductor substrate 42 is controlled to about 4 7 5 · ◦, the effect of reducing the gas content is better. After the required titanium nitride layer 56 is formed, an insulating layer 58 may be formed to cover the entire titanium nitride layer 56 and cover the entire capacitor structure. The present invention has many advantages. The paper size from Denso is applicable to the national standard (CNS) A4 specification (0 x 297 public love) 1 --------- _ 4 410 0 A7 B7 V. Description of the invention () System to reduce titanium argon The gas content in the layer will effectively reduce the impurities in the vaporized titanium layer content. In this way, it is possible to reduce the electrical resistance of the vaporized convergence layer formed. It can also improve its conductive properties, which in turn improves the operational performance of the titanium nitride formed. Secondly, by using the method provided by the present invention to manufacture the atmosphere & layer ', the thermal I budget of the entire process can be greatly reduced. Compared with the traditional technology, cypress reduces the gas content in the titanium nitride layer by introducing NH3 gas and maintaining the temperature above 650 ° C. In the method provided by the present invention, since the hydrogen atom group can interact with the gas in the titanium nitride layer in a lower temperature environment, HC1 is formed and eliminated by an air extractor. Therefore, it is obvious that when using the related process of the present invention, heat consumption can be effectively reduced. In particular, in order to effectively reduce the gas content in the titanium nitride layer, placing the entire semiconductor substrate in an environment with a temperature higher than 65 ° C. for a long time often tends to cause other components previously formed on the semiconductor substrate to be subjected to Considerable damage, leading to a significant decline in the operating performance of the entire semiconductor integrated circuit. In addition, due to the reduction of the gas content in the titanium nitride layer, its conductive properties can be greatly improved. Titanium nitride is used as the capacitor electrode plate When used, it can effectively reduce the leakage current of the entire capacitor and the structure during operation due to the reduction of the gas content. In addition, when using the method of the present invention to reduce the gas content, due to the use of a remote plasma system (RPS) temperature is higher than the standard of this paper. Applicable to China National Standard (CNS) A4 specification (210 X 297 public love) (Please read the precautions on the back before filling this page) -1 I ----- Order-- -11 I-- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7_ V. Description of the invention () The traditional technology (about 65 ~ 680 deaths) is low, so it can also effectively prevent the rise of titanium nitride The effect can also be 囡 0 layer film it. Its rate to good dispersion of the expansion path, if the chromosomal miscellaneous gas in the middle half of the layer in order to clear the hair in this example, the actual body hair and hair look out Limit, in order to use 0 疋 JIΓ 0 and its example is T, in fact, it is so clear to explain the scope of the work within the scope of the package should be modified. Fan Mingli ’s special encyclopedia, please leave Shentou The following are not described (please read the precautions on the back before filling this page)

* ----------- I-I Line Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

A8B8C8D8 4410 0 1 6. Scope of patent application 1. A method for forming a titanium halide layer on a semiconductor substrate, the method includes at least the following steps: using a chemical vapor deposition method to form a titanium nitride layer on the semiconductor substrate; Hydrogen-containing atoms are trapped so as to form gaseous hydrogen gas with the gas impurities in the titanium argon layer to reduce the content of gas impurities in the titanium nitride layer, wherein the hydrogen-containing atom group is a remote plasma A system (reinote piasma system; RPS) is formed by dissociating a hydrogen-containing gas, and the gas in the titanium nitride layer will diffuse to the surface of the titanium nitride layer and combine with the hydrogen-containing atomic group. 2. The method of claim 1 in the patent scope, in which the above procedure for forming a titanium nitride layer is formed by using titanium tetrachloride (TiCl4) as a reaction gas. 3. The method according to item 1 of the patent application, wherein the reaction gas for forming the titanium nitride layer includes at least titanium tetraoxide (TiC14), argon (NH3) and hydrogen (H2). 4. For the method of applying for item No. 丨, the hydrogen-containing gas can be selected from Η ;, ΝΗ3, or any combination thereof. 5. For the method of applying for item 1 of the patent scope, wherein the above-mentioned hydrogen-containing gas is passed into the first reaction chamber, and the hydrogen-containing gas is electrically numbered. The paper size applies the Chinese National Standard (CNS) A4 specification. (210 X 297 cm) I ------------------ ^-f < Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives οο T- 4 4 VI. The scope of the patent application process will generate neutral hydrogen-containing atomic groups. 6. The method according to item 5 of the patent application, wherein the nitrogen-containing atom rhenium is introduced into a second reaction chamber, and the semiconductor substrate is heated in the second reaction chamber to 250 to 650. 〇 so that the gas in the titanium nitride layer reacts with the hydrogen-containing atomic group. 7. The method of claim 5 in the scope of patent application, which further includes connecting a pump to the second reaction chamber, so as to remove the generated hydrogenated gas from the second reaction chamber and remove . 8. The method according to item 1 of the scope of patent application, wherein when the hydrogen-containing gas is subjected to plasma dissociation using the Shangsui remote plasma system, the power applied is about 2000 to 4000 Watt »9. If the patent is applied for The method of Fanyuan No. 1 wherein the above-mentioned procedure for forming a nitrided material layer is performed under an environment at a temperature of about 350 to 500 ° C. 10.-A method for forming a titanium nitride layer on a semiconductor substrate The method includes at least the following steps: forming a titanium nitride layer on a semiconductor substrate using a chemical vapor deposition method; and performing a plasma process on a hydrogen-containing gas in a first reaction chamber to generate dissociated radicals (radical) ; This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) C Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives i κ ----- --- ^ --------- ^ --------------------------- ^ Bcs & 41 00 1 VI. The scope of the patent application is in the second reaction chamber. The semiconductor substrate is heated to a temperature of about 250 to 650 ° C, and the hydrogen-containing atom is trapped in order to communicate with the substrate. The gas in the titanium nitride layer reacts to generate a hydrogenated gas. The gas located in the titanium nitride layer will diffuse toward the surface of the titanium nitride layer and combine with the hydrogen-containing atomic group to reduce the nitrogen. The gas content in the titanium layer; and the formed hydrogen gas is removed from the second reaction chamber. 11_ The method according to item 10 of the scope of patent application, wherein the above procedure for forming a titanium nitride layer is formed by using titanium tetrachloride (TiCl4) as a reaction gas. 12. The method according to item 10 of the patent application, wherein the hydrogen-containing gas can be selected from H2, NH3 or any combination thereof. 13. The method according to item 10 of the patent application range, wherein in the first reaction chamber described above, the power of the plasma dissociation process of the argon-containing gas is about 2000 to 4000 Watt. 14. A method of forming a capacitor having a top electrode of a titanium nitride layer, the method comprising at least the following steps: forming a dielectric layer on a semiconductor substrate; etching the dielectric layer to form a contact hole in the dielectric layer, and The upper surface of the semiconductor substrate is exposed; this paper size applies to the Chinese National Standard (CNS) A4 specification (210 x 297 public love) — It --- I I --- *-II In II ^ «— — It — — ——-VJ, (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 4 0 0 VI. The patent application scope forms a conductive plug in the contact hole to connect Located on the semiconductor substrate; (Please read the precautions on the back before filling this page) Form a conductive layer on the top surface of the dielectric layer and the conductive plug to serve as the bottom electrode of the capacitor, and be electrically connected to the conductive plug Forming a capacitor dielectric layer on the surface of the conductive layer; and forming a titanium nitride layer on the surface of the capacitor dielectric layer to serve as the top electrode of the capacitor, wherein the titanium nitride layer uses a chemical vapor deposition method (CVD) is formed, and by introducing an atomic group containing argon to form gaseous hydrogen gas with the gas impurities in the titanium nitride layer, the content of gas impurities in the titanium nitride layer is reduced, wherein the hydrogen containing The atomic group is formed by dissociating a hydrogen-containing gas using a remote plasma system (RPS), and the gas located in the titanium nitride layer will diffuse toward the surface of the titanium nitride layer, and The combination of the hydrogen-containing atomic group ° 15. The electrical method according to item 4 of the patent application scope, wherein after the conductive layer is formed, hemispherical silicon ^ gj (Hemi-Sphericai Grain, H SG) can be formed on the conductive layer. Surface to increase area. m Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 16. For the method of item I4 of the scope of patent application, the above capacitor dielectric layer can be selected from Ta205, 0 / N, 0 / N / 0, or any combination thereof. 0 This paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) A8B8§ 6. Scope of patent application The above conductive layer can be selected from doped a-silicon and synchronously doped amorphous In-situ doped a-silicon or any combination thereof. 18. The method according to item 14 of the patent application scope, wherein the reaction gas for forming the titanium nitride layer includes at least titanium tetrachloride (TiCl4), ammonia (NH3), and hydrogen (H2). 19. The method according to item 14 of the scope of patent application, wherein the hydrogen-containing gas is passed into the first reaction chamber, and a neutral hydrogen-containing atomic group is generated by plasma-treating the hydrogen-containing gas. 20. The method of claim 19, wherein the hydrogen-containing atomic group is introduced into a second reaction chamber, and the semiconductor substrate is heated in the second reaction chamber to a temperature of 25 to 650 ° C so as to be located at The gas in the titanium nitride layer reacts with the hydrogen-containing atomic group. 21. The method according to item 14 of the patent application, wherein when the above-mentioned remote plasma system is used for plasma dissociation of the hydrogen-containing gas, the power applied is about 2000 to 4000 Watt. — II I ---- I 3 ^ ------ ί Order --------- line --- <-* {Please read the unintentional matter on the back before filling this page) Consumption cooperation between employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed paper standards applicable to national standards (CNS) A4 specifications < 210 * 297 mm>