Thin film material and preparation method thereof, and graphite boat carrier and preparation method thereof

Abstract

The invention provides a thin film material and a preparation method thereof, and a graphite boat carrier and a preparation method thereof, a new thin film material is developed, the thin film material comprises a SixNyPoly-Siz thin film and / or a SixNyPoly-Siz: H thin film, and the ratio of the mass sum of the Si element and the N element in the thin film material to the total mass of all elements contained in the thin film material is less than or equal to 100 wt%, and the ratio of the mass sum of the Si element and the N element in the thin film material to the total mass of all the elements contained in the thin film material is less than or equal to 100 wt%. The thin film material has the characteristic of good stability, so that the stability of the thin film on the surface of the graphite boat carrier can be improved in a saturated covering boat plating process on the surface of the graphite boat carrier.

Description

Technical Field

[0001] The present invention relates to the field of solar cells, and in particular to a thin film material and a preparation method thereof, as well as a graphite boat carrier and a preparation method thereof. Background Art

[0002] At present, in the production process of solar cells, tubular PECVD (Plasma Enhanced Chemical Vapor Deposition) is usually used for solar cell coating. When coating, the carrier of the cell is usually a graphite boat. After the carrier graphite boat is used many times, a conductive film will accumulate on the surface of the graphite boat. The conductive film deposited on the graphite boat needs to be cleaned offline. After the cleaning is completed, a saturated coating boat process is generally used on the surface of the graphite boat.

[0003] However, the film deposited by the existing graphite boat surface saturation coverage plating boat process has poor stability. After the plating boat is put into operation, it seriously affects the yield and efficiency of the battery cell coating. Summary of the invention

[0004] The present application provides a thin film material and a preparation method thereof, as well as a graphite boat carrier and a preparation method thereof, which can solve the problem of poor stability of the thin film.

[0005] In order to solve the above technical problems, a technical solution adopted in this application is: to provide a thin film material, including Si x N y Poly-Si z Thin film and / or Si x N y Poly-Si z :H film; and the mass of the Si element and the N element in the thin film material, the ratio of the total mass of all elements contained in the thin film material is less than or equal to 100wt%.

[0006] In one embodiment, the Si x N y Poly-Si z Thin films and a-Si:H thin films; or

[0007] The Si stacking arrangement x N y Poly-Si z :H film and a-Si:H film.

[0008] In one embodiment, the Si x N y Poly-Si zThin film, the Si x N y Poly-Si z :H film and a-Si:H film.

[0009] In one embodiment, the thickness of the thin film material is 5 nm-6 μm.

[0010] In order to solve the above technical problems, another technical solution adopted in the present application is: to provide a method for preparing a thin film material, comprising:

[0011] placing a growth substrate in the reaction chamber;

[0012] A reaction gas is introduced into the reaction chamber and ionized into plasma by radio frequency discharge, wherein the reaction gas includes SiH4 and N2.

[0013] In one embodiment, in the step of introducing a reaction gas into the reaction chamber, the reaction gas consists of SiH 4 and N 2 .

[0014] In one embodiment, in the step of introducing a reaction gas into the reaction chamber, the reaction gas consists of SiH 4 , N 2 and H 2 .

[0015] In one embodiment, the step of introducing a reaction gas into the reaction chamber and ionizing plasma by radio frequency discharge specifically includes any two of the following three steps:

[0016] A first reaction gas is introduced into the reaction chamber, and a first plasma is ionized by radio frequency discharge; the first reaction gas is composed of SiH4 and N2;

[0017] A second reaction gas is introduced into the reaction chamber, and a second plasma is ionized by radio frequency discharge; the second reaction gas is composed of SiH4, N2 and H2;

[0018] A third reaction gas is introduced into the reaction chamber, and a third plasma is ionized by radio frequency discharge; the third reaction gas is composed of SiH4 and H2.

[0019] In one embodiment, the step of introducing a reaction gas into the reaction chamber and ionizing plasma by radio frequency discharge specifically includes the following three steps:

[0020] A first reaction gas is introduced into the reaction chamber, and a first plasma is ionized by radio frequency discharge; the first reaction gas is composed of SiH4 and N2;

[0021] A second reaction gas is introduced into the reaction chamber, and a second plasma is ionized by radio frequency discharge; the second reaction gas is composed of SiH4, N2 and H2;

[0022] A third reaction gas is introduced into the reaction chamber, and a third plasma is ionized by radio frequency discharge; the third reaction gas is composed of SiH4 and H2.

[0023] In one embodiment, the method is performed using PECVD equipment; wherein,

[0024] The temperature of the reaction chamber is 350-480°C;

[0025] The pressure of the reaction chamber is 400-500Pa;

[0026] The flow rate of SiH4 is 500-10000sccm;

[0027] The flow rate of N2 is 1000-20000sccm;

[0028] The discharge power of the PECVD equipment is 0-40KW;

[0029] The duty cycle of the radio frequency power supply of the PECVD device: 0-100 / 1-1000ms;

[0030] The process time of the PECVD equipment is 0-10H.

[0031] In one embodiment, the method is performed using PECVD equipment; wherein,

[0032] The temperature of the reaction chamber is 300-480°C;

[0033] The pressure of the reaction chamber is 250-600 Pa;

[0034] The flow rate of SiH4 is 500-10000sccm;

[0035] The flow rate of N2 is 1000-20000sccm;

[0036] The flow rate of H2 is 1000-20000sccm;

[0037] The discharge power of the PECVD equipment is 0-40KW;

[0038] The duty cycle of the radio frequency power supply of the PECVD device: 0-100 / 1-1000ms;

[0039] The process time of the PECVD equipment is 0-10H.

[0040] In order to solve the above technical problems, another technical solution adopted in the present application is: to provide a method for manufacturing a graphite boat carrier, comprising:

[0041] A thin film is deposited on a graphite boat using any one of the above-mentioned methods for preparing a thin film material.

[0042] In order to solve the above technical problems, another technical solution adopted in the present application is to provide a graphite boat carrier, comprising:

[0043] Graphite boat;

[0044] An isolation film, covering the surface of the graphite boat;

[0045] Wherein, the isolation film is any one of the film materials described above; or the isolation film is a film material deposited on the graphite boat using any one of the preparation methods described above.

[0046] Different from the prior art, the thin film material and the preparation method thereof, as well as the graphite boat carrier and the preparation method thereof provided in the present application, develop a new thin film material, and the thin film material includes Si x N y Poly-Si z Thin film and / or Si x N y Poly-Si z :H film, the film material has the characteristic of good stability, thereby, in the saturation coverage plating boat process on the surface of the graphite boat, it can improve the stability of the film on the surface of the graphite boat carrier. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 It is a structural schematic diagram of a graphite boat carrier provided in one embodiment of the present application;

[0048] Figure 2 It is a schematic flow chart of a method for preparing a thin film material provided in one embodiment of the present application;

[0049] Figure 3 yes Figure 2 A schematic flow chart of an embodiment of step S2;

[0050] Figure 4 yes Figure 2 A schematic flow chart of another embodiment of step S2;

[0051] Figure 5 yes Figure 2 A schematic flow chart of another embodiment of step S2;

[0052] Figure 6 yes Figure 2A schematic flow chart of another embodiment of step S2;

[0053] Fig. 7A This is an EDS characterization diagram of a thin film prepared by SiH4 and H2 under certain conditions in this application;

[0054] Figure 7B This is an EDS characterization diagram of a thin film prepared by SiH4 and N2 under certain conditions in this application;

[0055] Figure 7C This application uses SiH4, N2 and H2 to prepare the film under certain conditions. EDS characterization diagram;

[0056] Figure 8 XRD patterns of different films provided in this application. DETAILED DESCRIPTION

[0057] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0058] The terms "first", "second", "third" in this application are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined as "first", "second", "third" can expressly or implicitly include at least one of the features. In the description of this application, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined. In the embodiments of this application, all directional indications (such as up, down, left, right, front, back...) are only used to explain the relative position relationship, movement, etc. between the components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication also changes accordingly. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device comprising a series of steps or units is not limited to the steps or units listed, but optionally also includes steps or units that are not listed, or optionally also includes other steps or units inherent to these processes, methods, products or devices.

[0059] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0060] The present application is described in detail below with reference to the accompanying drawings and embodiments.

[0061] See also Figure 1 , Figure 1 1 is a schematic diagram of a graphite boat carrier provided in an embodiment of the present application. Specifically, the present application provides a graphite boat carrier 100 , and the graphite boat carrier 100 includes a graphite boat sheet 10 and an isolation film 20 .

[0062] The number of the graphite boat sheets 10 can be one or more, and when the number of the graphite boat sheets 10 is more than one (not shown), the multiple graphite boat sheets 10 are arranged in parallel and are connected in series by a number of graphite rods, ceramic rods and nuts and then fastened.

[0063] In the related art, a saturated coating boat process is performed on the surface of the graphite boat sheet 10 to improve the influence of the graphite boat carrier 100 on the coating process. Specifically, the saturated coating boat process on the surface of the graphite boat sheet 10 has the following advantages:

[0064] 1. It can effectively improve the influence of the graphite boat carrier 100 on the coating process and improve production efficiency and yield rate;

[0065] 2. It helps the graphite boat carrier 100 to distribute heat more evenly during the heating process, so that the silicon wafer is heated more uniformly, thereby improving battery performance;

[0066] 3. Protect the graphite boat sheet 10, reduce corrosion and wear, thereby extending the service life of the graphite boat carrier 100 and reducing production costs.

[0067] However, the prior art uses silicon nitride (SiN) film to perform saturation coating on the surface of the graphite boat carrier, which has at least one of the following disadvantages:

[0068] 1. When the silicon nitride film is plated on the surface of the graphite boat carrier, a large amount of dust will be generated, causing a large amount of dust to accumulate and fall inside the furnace tube, shortening the maintenance cycle of the furnace tube.

[0069] 2. A silicon nitride film is plated on the surface of the graphite boat carrier. After the graphite boat carrier is put into use, there are problems such as low efficiency of the first boat and a high rate of EL bad black spots.

[0070] 3. A silicon nitride film is coated on the surface of the graphite boat carrier. After the graphite boat carrier is put into use, the color of the graphite boat carrier is uneven in the first ten coating cycles.

[0071] To solve the above problems, the present application provides a new film material as an isolation film 20, which replaces the silicon nitride film to perform a surface saturation coating process on the graphite boat sheet 10. Specifically, the isolation film 20 covers the surface of the graphite boat sheet 10 and includes Si x N y Poly-Si z Thin film and / or Si x N y Poly-Si z :H film.

[0072] Specifically, the values ​​of x, y, and z can be the same or different. The isolation film 20 at least includes silicon nitride (SiN) crystals and polycrystalline silicon (Poly-Si) crystals. x N y Poly-Si z :H film and Si x N y Poly-Si z The structure of the film is basically the same, the difference is that Si x N y Poly-Si z :H film is doped with H element to control and change the proportion of various elements.

[0073] The ratio of the sum of the mass of Si element and N element in the isolation film 20 (film material) to the total mass of all elements contained in the isolation film 20 is less than or equal to 100 wt %.

[0074] For example, among all the elements contained in the isolation film 20 , the mass sum of the Si element and the N element accounts for 80%, 90%, 95% or 100%.

[0075] It can be understood that when the isolation film 20 only includes Si element and N element, the sum of the mass of Si element and N element is equal to 100%.

[0076] When the isolation film 20 contains other elements besides Si and N, for example, when impurities such as O, P and / or C are doped during the preparation process, the sum of the mass of Si and N is less than 100%.

[0077] Specifically, the present application provides an isolation film 20, including Si x N y Poly-Si z Thin film and / or Six N y Poly-Si z :H film, the thermal deformation of the film layer of the isolation film 20 and the POLY process (Polysilicon process) of the solar cell is basically close, and has at least one beneficial effect: 1) It can significantly improve the cracking and peeling phenomenon of the film layer on the surface of the graphite boat carrier 100; 2) The impedance of the graphite boat carrier 100 formed after the isolation film 20 is plated on the surface of the graphite boat sheet 10 is highly matched with the POLY process of the solar cell when the graphite boat carrier 100 is used for the first time, and the stability of the film layer grown by the process is good, and the efficiency and yield of the coating will not be lost; 3) The graphite boat carrier 100 provided in the present application significantly improves the appearance color of the graphite boat carrier 100 during the first 1-10 processes.

[0078] In some embodiments, the isolation film 20 may include only Si x N y Poly-Si z film.

[0079] In some embodiments, the isolation film 20 may include only Si x N y Poly-Si z :H film.

[0080] In some embodiments, the isolation film 20 may include a stacked Si x N y Poly-Si z Thin Film and Si x N y Poly-Si z :H film.

[0081] In some embodiments, the isolation film 20 may include a stacked Si x N y Poly-Si z Thin film and a-Si:H thin film. Among them, a-Si:H thin film is an amorphous silicon thin film doped with H element.

[0082] In some embodiments, the isolation film 20 includes a stacked Si x N y Poly-Si z :H film and a-Si:H film.

[0083] In some embodiments, the isolation film 20 includes a stacked Si x N y Poly-Si z Thin film, Si x Ny Poly-Si z :H film and a-Si:H film.

[0084] In the above embodiments, when the film layers in the isolation film 20 are multiple layers, the stacking order of the film layers can be freely set and is not limited here.

[0085] Specifically, since the isolation film 20 provided in any of the above embodiments contains at least Si x N y Poly-Si z Thin Film and Si x N y Poly-Si z :H film, therefore, the graphite boat carrier 100 formed by coating the above-mentioned isolation film 20 on the graphite boat sheet 10 has at least one beneficial effect: 1) it can significantly improve the cracking and peeling phenomenon of the film layer on the surface of the graphite boat carrier 100; 2) it has a high matching performance with the POLY process of the solar cell, and the film layer grown by the process has good stability without losing efficiency and yield; 3) it can significantly improve the appearance color of the graphite boat carrier 100 during the first 1-10 processes.

[0086] The thickness of the isolation film 20 is 5 nm-6 μm. For example, the thickness of the isolation film 20 can be 5 nm, 500 nm, 1 μm, 3 μm or 6 μm, etc., which is not limited here and can be selected according to needs.

[0087] In some embodiments, the graphite boat carrier 100 is a single saturated graphite boat carrier 100 (the film layer in the isolation film 20 is one layer), and the thickness of the isolation film 20 is 0.5-3 μm.

[0088] In some embodiments, the graphite boat carrier 100 is a mixed film saturated graphite boat carrier 100 (the film layer in the isolation film 20 is multi-layered), and the isolation film 20 includes a stacked Si x N y Poly-Si z Thin film, Si x N y Poly-Si z :H film and a-Si:H film, in the isolation film 20, Si x N y Pol y -Si z Thin film, Si x N y Poly-Si z The thickness ratio of the Si:H film and the a-Si:H film can be 2:2:1. x Ny Poly-Si z The thickness of the film can be 0.2-1.2μm; Si x N y Poly-Si z The thickness of the Si:H film can be 0.2-1.2 μm; the thickness of the a-Si:H film can be 0.1-0.6 μm.

[0089] In some embodiments, the isolation film 20 includes a stacked Si x N y Poly-Si z film and a-Si:H film, isolation film 20, Si x N y Poly-Si z The thickness ratio of the film and the a-Si:H film can be 2:1. x N y Poly-Si z The thickness of the film can be 0.2-1.2 μm; the thickness of the a-Si:H film can be 0.1-0.6 μm.

[0090] In some embodiments, the isolation film 20 includes a stacked Si x N y Poly-Si z :H film and a-Si:H film, in the isolation film 20, Si x N y Poly-Si z The thickness ratio of the Si:H film to the a-Si:H film can be 4:1. x N y Poly-Si z The thickness of the Si:H film can be 0.4-2.4 μm; the thickness of the a-Si:H film can be 0.1-0.6 μm.

[0091] Specifically, in the above-mentioned embodiments, the thickness configuration of each film layer in the isolation film 20 is mainly designed based on the formula that produces the least powder when saturated in the actual application process and performs the most stable performance in combination with the POLY process after the graphite boat carrier 100 is put into production. Based on actual needs, it can be selected according to actual needs.

[0092] Specifically, the present application also provides a new thin film material preparation process. Specifically, the present application takes the deposition of an isolation film 20 on the surface of a graphite boat sheet 10, and the present application takes the isolation film 20 replacing the silicon nitride film to perform a saturated coating process on the surface of the graphite boat sheet 10 as an example to illustrate.

[0093] See also Figure 2 , Figure 2 : is a schematic diagram of a process for preparing a thin film material provided by an embodiment of the present application. The present application also provides a method for preparing a thin film material, comprising:

[0094] Step S1: placing a growth substrate in a reaction chamber.

[0095] In the embodiment of the present application, the growth substrate is a graphite boat carrier. Of course, in other embodiments, the growth substrate can be replaced according to the application scenario, which is not limited here.

[0096] In the embodiment of the present application, the reaction equipment is a PECVD equipment, and the reaction chamber is a reaction chamber in the PECVD equipment.

[0097] Step S2: introducing reaction gas into the reaction chamber and ionizing plasma by radio frequency discharge, wherein the reaction gas includes SiH4 and N2.

[0098] In one embodiment, before step S2, the reaction chamber may be preheated to evaporate the residual water vapor in the growth substrate and the chamber to prevent the water vapor from affecting the film quality and equipment safety during the subsequent vacuum coating process. In addition, preheating the reaction chamber can make the temperature distribution of the graphite boat more uniform, which is crucial for obtaining a uniform thin film coating. It can also reduce stress, relieve the thermal stress caused by rapid temperature changes in the graphite boat, avoid material deformation or damage, and ensure the stability of the coating process.

[0099] In one embodiment, after preheating the reaction chamber, leak detection is required to detect whether the water vapor in the reaction chamber is completely eliminated and whether there is a risk of gas leakage in the reaction chamber. These defects may cause gas leakage in the subsequent thin film deposition process, affecting the uniformity and yield of the thin film.

[0100] In one embodiment, after leak detection, the reaction chamber may be pretreated with NH3 to improve the adhesion of subsequent thin film growth. Specifically, NH3 gas of a certain concentration and flow rate is introduced into the reaction chamber. As a reducing gas, NH3 can react with oxides that may exist on the chamber wall or the surface of the graphite boat to form a more stable nitride layer, thereby cleaning the surface and providing a good nucleation condition for subsequent thin film deposition, thereby improving the adhesion of subsequent thin film growth.

[0101] It should be noted that the duration of NH3 pretreatment needs to be adjusted according to actual needs to ensure sufficient surface modification without over-treatment to damage the graphite boat or affect the quality of the film. After the pretreatment, it is necessary to vacuum and exhaust again to remove the residual NH3 and other reaction by-products to prepare for the next formal coating step.

[0102] After the reaction chamber is preheated, leak-checked, and pre-treated with NH3, reaction gases including SiH4 and N2 are introduced into the reaction chamber.

[0103] Specifically, the plasma formed after the reaction gas is ionized is used to deposit Si on the surface of the graphite boat. x N y Poly-Si z Thin film or Si x N y Poly-Si z :H film.

[0104] In one embodiment, in the step of introducing the reaction gas into the reaction chamber, the reaction gas is composed of SiH4 and N2, so that the plasma formed after the reaction gas is ionized is used to form Si x N y Poly-Si z film.

[0105] In another embodiment, in the step of introducing the reaction gas into the reaction chamber, the reaction gas is composed of SiH4, N2 and H2, so that the plasma formed after the reaction gas is ionized is used to form Si x N y Poly-Si z :H film.

[0106] It should be noted that in this application, N2 is used as the N source because of the insufficiency of plasma activation, Si ion enrichment, and the growth of Si during the reaction. x N y At the same time as the crystal, Poly-Si crystal is grown synchronously, forming a special Si x N y Poly-Si z When the reaction gas includes SiH4, N2 and H2, H-doped Si x N y Poly-Si z Thin film, namely Si x N y Poly-Si z :H film.

[0107] However, if NH3 is used as the N source, due to the characteristics of plasma chemical vapor deposition, NH3 is fully ionized and combines with Si ions to form SiN crystals, but Poly-Si crystals cannot be formed.

[0108] If N2O is used as the N source, SiO2 film will be directly generated due to the enrichment of O negative ions, and Si x N yPoly-Si z film.

[0109] Specifically, in the preparation method provided in the present application, a reaction gas including SiH4 and N2 is introduced into the reaction chamber, and a plasma formed after the reaction gas is ionized is used to form Si x N y Poly-Si z Thin film or Si x N y Poly-Si z :H film, Si x N y Poly-Si z Thin Film and Si x N y Poly-Si z :H film has the characteristic of good stability, thus, in the saturation coverage plating boat process on the surface of the graphite boat carrier, the stability of the surface state of the graphite boat carrier can be improved.

[0110] See also Figure 3 , Figure 3 yes Figure 2 Schematic diagram of a flow chart of an embodiment of step S2 in FIG. 1 , in one embodiment, step S2 includes:

[0111] Step S21: introducing a first reaction gas into the reaction chamber and ionizing a first plasma by radio frequency discharge; the first reaction gas is composed of SiH4 and N2.

[0112] Specifically, the first plasma formed in step S21 is used to form Si x N y Poly-Si z film.

[0113] Step S22: introducing a second reaction gas into the reaction chamber and ionizing a second plasma by radio frequency discharge; the second reaction gas is composed of SiH4, N2 and H2.

[0114] Specifically, the second plasma formed in step S22 is used to form Si x N y Poly-Si z :H film.

[0115] It should be noted that in the embodiment of the present application, step S21 may be before or after step S22. When step S21 is before step S22, Si is first formed on the reaction substrate. x N y Poly-Si z The film is then formed into Si xN y Poly-Si z After the film is formed on the substrate x N y Poly-Si z :H film. When step S21 is after step S22, Si is first formed on the reaction substrate. x N y Poly-Si z :H film, and then form Si x N y Poly-Si z :H film formed on the substrate x N y Poly-Si z film.

[0116] See also Figure 4 , Figure 4 yes Figure 2 A flow chart of another embodiment of step S2 in FIG. 1 ; in one embodiment, step S2 includes:

[0117] Step S21: introducing a first reaction gas into the reaction chamber and ionizing a first plasma by radio frequency discharge; the first reaction gas is composed of SiH4 and N2.

[0118] Specifically, the first plasma formed in step S21 is used to form Si x N y Poly-Si z film.

[0119] Step S23: introducing a third reaction gas into the reaction chamber and ionizing a third plasma by radio frequency discharge; the third reaction gas is composed of SiH4 and H2.

[0120] Specifically, the third plasma is used to form an a-Si:H film. x N y Poly-Si z Thin film and Si x N y Poly-Si z :H films have similar performances and can improve the stability of the film on the surface of the graphite boat carrier.

[0121] Among them, step S23 can be before or after step S21.

[0122] See also Figure 5 , Figure 5 yes Figure 2FIG. 1 is a flow chart of another embodiment of step S2 in FIG. 1 ; in one embodiment, step S2 includes:

[0123] Step S22: introducing a second reaction gas into the reaction chamber and ionizing a second plasma by radio frequency discharge; the second reaction gas is composed of SiH4, N2 and H2.

[0124] Specifically, the second plasma formed in step S22 is used to form Si x N y Poly-Si z :H film.

[0125] Step S23: introducing a third reaction gas into the reaction chamber and ionizing a third plasma by radio frequency discharge; the third reaction gas is composed of SiH4 and H2.

[0126] Specifically, the third plasma is used to form an a-Si:H film. x N y Poly-Si z Thin film and Si x N y Poly-Si z :H films have similar performances and can improve the stability of the film on the surface of the graphite boat carrier.

[0127] Among them, step S23 can be before or after step S22.

[0128] See also Figure 6 , Figure 6 yes Figure 2 FIG. 1 is a flow chart of another embodiment of step S2 in FIG. 1 ; in one embodiment, step S2 includes:

[0129] Step S21: introducing a first reaction gas into the reaction chamber and ionizing a first plasma by radio frequency discharge; the first reaction gas is composed of SiH4 and N2.

[0130] Specifically, the first plasma formed in step S21 is used to form Si x N y Poly-Si z film.

[0131] Step S22: introducing a second reaction gas into the reaction chamber and ionizing a second plasma by radio frequency discharge; the second reaction gas is composed of SiH4, N2 and H2.

[0132] Specifically, the second plasma formed in step S22 is used to form Si x N yPoly-Si z :H film.

[0133] Step S23: introducing a third reaction gas into the reaction chamber and ionizing a third plasma by radio frequency discharge; the third reaction gas is composed of SiH4 and H2.

[0134] Specifically, the third plasma is used to form an a-Si:H film. x N y Poly-Si z Thin film and Si x N y Poly-Si z :H films have similar performances and can improve the stability of the film on the surface of the graphite boat carrier.

[0135] Among them, step S23 can be before or after step S21, or before or after step S22, which is not limited here.

[0136] That is, among the thin film materials, a-Si:H thin film, Si x N y Poly-Si z Thin film and Si x N y Poly-Si z :H The stacking order of the thin films is not limited.

[0137] In each embodiment of the above preparation method, the temperature of the reaction chamber is 350-480° C. For example, the temperature of the reaction chamber can be 350° C., 420° C., or 480° C., etc., which is not limited here.

[0138] It should be noted that too high or too low temperature will affect the coating effect. For example, when the temperature of the reaction chamber is lower than 350°C, serious powder discharge will occur during the coating process; when the temperature of the reaction chamber exceeds 480°C, the film has been modified under high temperature conditions.

[0139] The pressure of the reaction chamber is 250-600 Pa. For example, the pressure of the reaction chamber may be 400 Pa, 450 Pa or 500 Pa, etc., which is not limited here.

[0140] It should be noted that too high or too low pressure will affect the coating effect. For example, when the pressure is less than 400Pa, uneven film growth and bulging will occur. When the pressure is greater than 500Pa, serious powder discharge will occur during the coating process.

[0141] When the reaction gas includes SiH 4 , the flow rate of SiH 4 is 500-10000 sccm. For example, the flow rate of SiH 4 can be 500 sccm, 1000 sccm, 3000 sccm, 5000 sccm, 7000 sccm or 10000 sccm, etc., which is not limited here.

[0142] When the reaction gas includes N2, the flow rate of N2 is 1000-20000 sccm. For example, the flow rate of N2 can be 1000 sccm, 5000 sccm, 10000 sccm, 12000 sccm, 15000 sccm or 20000 sccm, etc., which is not limited here.

[0143] When the reaction gas includes H2, the flow rate of H2 is 1000-20000 sccm. For example, the flow rate of H2 can be 1000 sccm, 5000 sccm, 10000 sccm, 12000 sccm, 15000 sccm or 20000 sccm, etc., which is not limited here.

[0144] When the PECVD device ionizes the above-mentioned reaction gases by radio frequency discharge, the discharge power of the PECVD device is 0-40KW. For example, the discharge power of the PECVD device can be 1KW, 5KW, 10KW, 20KW, 30KW, or 40KW, etc. Specifically, the discharge power of the PECVD device is determined by the size of the growth substrate and the power density, which is not limited here.

[0145] The duty cycle of the RF power supply of the PECVD device is 0-100 / 1-1000ms. Specifically, the PECVD device adopts pulsed discharge. In one cycle, the RF power supply can be turned on for 0-100ms and turned off for 1-1000ms, and the cycle repeats. For example, the duty cycle of the RF power supply of the PECVD device can be 3 / 36, 4 / 52, 6 / 60, 6 / 108, 20 / 600 or 40 / 800, etc. Specifically, the duty cycle of the RF power supply of the PECVD device is determined according to the size and power density of the growth substrate, and is not limited here.

[0146] The process time of the PECVD equipment is 0-10 hours. For example, the process time of the PECVD equipment can be 1 hour, 3 hours, 5 hours, 7 hours or 10 hours, etc., which is not limited here.

[0147] Finally, after the thin film material is formed, the PECVD equipment is purged with nitrogen, and then the vacuum is broken before the boat is taken out.

[0148] Specifically, in the preparation method provided in the present application, a reaction gas including SiH4 and N2 is introduced into the reaction chamber, and a plasma formed after the reaction gas is ionized is used to form Si x N y Poly-Si z Thin film or Si x N y Poly-Si z :H film, and a reaction gas including SiH4 and H2 is introduced into the reaction chamber, and the plasma formed after SiH4 and H2 are ionized is used to form an a-Si:H film. x N y Poly-Si z Thin film and / or Si x N y Poly-Si z :H film, or Si x N y Poly-Si z Thin film and / or Si x N y Poly-Si z :H film is formed by combining with a-Si:H film to form a thin film material with the characteristic of good stability. When it is used in the saturated coverage plating boat process on the surface of a graphite boat carrier, that is, the thin film material is deposited on the graphite boat to form a surface coverage, and the thin film material is used as an isolation film. Since the thermal deformation of the isolation film and the film layer in the POLY process are basically similar, the film layer cracking and shedding phenomenon on the surface of the graphite boat carrier can be significantly improved. In addition, the graphite boat carrier formed after the graphite boat is plated with an isolation film has a high impedance matching with the POLY process when the first boat is online, and the film layer grown by the process has good stability without loss of efficiency and yield. Moreover, the graphite boat carrier provided in the present application significantly improves the appearance color of the graphite boat carrier during the first 1-10 processes.

[0149] The following are examples and comparative examples of the film materials provided in this application.

[0150] Example 1A:

[0151] The first reaction gas composed of SiH4 and N2 is introduced into the reaction chamber, the temperature of the reaction chamber is 400°C, the pressure of the reaction chamber is 400Pa, the flow rate of SiH4 is 3000sccm, the flow rate of N2 is 8000sccm, the discharge power of the PECVD equipment is 14KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 52ms, and the process time of the PECVD equipment is 4H.

[0152] Example 1B:

[0153] The parameters of Example 1B are substantially the same as those of Example 1A, except that the temperature of the reaction chamber is 350°C.

[0154] Example 1C:

[0155] The parameters of Example 1C are substantially the same as those of Example 1A, except that the temperature of the reaction chamber is 480°C.

[0156] Example 1D:

[0157] The parameters of Example 1D are substantially the same as those of Example 1A, except that the pressure of the reaction chamber is 400 Pa.

[0158] Example 1E:

[0159] The parameters of Example 1E are substantially the same as those of Example 1A, except that the pressure of the reaction chamber is 500 Pa.

[0160] Comparative Example 1A:

[0161] The parameters of Comparative Example 1A are substantially the same as those of Example 1A, except that the temperature of the reaction chamber is 250°C.

[0162] Comparative Example 1B:

[0163] The parameters of Comparative Example 1B are substantially the same as those of Example 1A, except that the temperature of the reaction chamber is 550°C.

[0164] Comparative Example 1C:

[0165] The parameters of Comparative Example 1C are substantially the same as those of Example 1A, except that the pressure of the reaction chamber is 200 Pa.

[0166] Comparative Example 1D:

[0167] The parameters of Comparative Example 1D are substantially the same as those of Example 1A, except that the pressure of the reaction chamber is 700 Pa.

[0168] Embodiment 2:

[0169] The parameters of Example 2 are substantially the same as those of Example 1, except that the first reaction gas introduced into the reaction chamber is replaced by a second reaction gas composed of SiH 4 , N 2 and H 2 .

[0170] Embodiment 3:

[0171] The parameters of Example 3 are basically the same as those of Example 1, except that the first reaction gas introduced into the reaction chamber is replaced by: a first reaction gas composed of SiH4 and N2, and a second reaction gas composed of SiH4, N2 and H2 are introduced into the reaction chamber in sequence. The first reaction gas is ionized into plasma by radio frequency discharge before another reaction gas is introduced.

[0172] Embodiment 4:

[0173] The parameters of Example 4 are basically the same as those of Example 1, except that the first reaction gas introduced into the reaction chamber is replaced by: a first reaction gas composed of SiH4 and N2, and a third reaction gas composed of SiH4 and H2 are introduced into the reaction chamber in sequence. The first reaction gas is ionized into plasma by radio frequency discharge before another reaction gas is introduced.

[0174] Embodiment 5:

[0175] The parameters of Example 5 are substantially the same as those of Example 1, except that the first reaction gas introduced into the reaction chamber is replaced by: a second reaction gas composed of SiH4, N2 and H2, and a third reaction gas composed of SiH4 and H2 are introduced into the reaction chamber in sequence. The first reaction gas introduced is ionized into plasma by radio frequency discharge before another reaction gas is introduced.

[0176] Embodiment 6:

[0177] The parameters of Example 6 are basically the same as those of Example 1, except that the first reaction gas introduced into the reaction chamber is replaced by: a first reaction gas composed of SiH4 and N2, a second reaction gas composed of SiH4, N2 and H2, and a third reaction gas composed of SiH4 and H2 are introduced into the reaction chamber in sequence. The first reaction gas is ionized into plasma by radio frequency discharge before another reaction gas is introduced.

[0178] Comparative Example 2:

[0179] The parameters of Comparative Example 2 are substantially the same as those of Example 1A, except that the reaction gas consists of SiH4 and NH3.

[0180] Comparative Example 3:

[0181] The parameters of Comparative Example 3 are substantially the same as those of Example 1A, except that the reaction gas consists of SiH4 and N2O.

[0182] The results of the above embodiments and comparative examples are shown in Table 1 below.

[0183] Table 1

[0184]

[0185]

[0186] It can be seen from Examples 1, 2, 3, 4, 5, and 6 in Table 1 that suitable process parameters are used to prepare Si x N y Poly-Siz Thin film, Si x N y Poly-Si z :H film and a-Si:H film, the film uniformity is qualified and there are no other abnormal problems. It can be seen from Example 1 and its comparative example that the process parameters outside the range are used to prepare Si x N y Poly-Si z Thin Film and Si x N y Poly-Si z :H film, there are various abnormalities such as powdering and bulging, and cannot be used normally. From Comparative Examples 2 and 3, it can be seen that according to the generally accepted knowledge in the industry, Comparative Example 2 prepared a silicon nitride film, and Comparative Example 3 prepared a silicon oxide film.

[0187] See also Figure 7A-7C , Fig. 7A This is an EDS characterization diagram of a thin film prepared by SiH4 and H2 under certain conditions in this application; Figure 7B This is an EDS characterization diagram of a thin film prepared by SiH4 and N2 under certain conditions in this application; Figure 7C This application uses EDS characterization diagrams of thin films prepared under certain conditions using SiH4, N2 and H2.

[0188] Among them, EDS (Energy-Dispersive X-ray Spectroscopy) is a commonly used material analysis technology, which is used to determine the type and content of elements in a sample.

[0189] in, Fig. 7A The preparation conditions of the EDS characterization diagram of the thin film shown are: a reaction gas composed of SiH4 and H2 is introduced into the reaction chamber, the temperature of the reaction chamber is 440°C, the pressure of the reaction chamber is 410Pa, the flow rate of SiH4 is 4300sccm, the flow rate of H2 is 9600sccm, the discharge power of the PECVD equipment is 13KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 50ms, and the process time of the PECVD equipment is 0.5H.

[0190] in, Figure 7B The preparation conditions of the EDS characterization diagram of the thin film shown are: a reaction gas composed of SiH4 and N2 is introduced into the reaction chamber, the temperature of the reaction chamber is 440°C, the pressure of the reaction chamber is 410Pa, the flow rate of SiH4 is 4300sccm, the flow rate of N2 is 12000sccm, the discharge power of the PECVD equipment is 13KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 50ms, and the process time of the PECVD equipment is 0.5H.

[0191] in, Figure 7C The preparation conditions of the EDS characterization diagram of the thin film shown are: a reaction gas composed of SiH4, N2 and H2 is introduced into the reaction chamber, the temperature of the reaction chamber is 440°C, the pressure of the reaction chamber is 410Pa, the flow rate of SiH4 is 4300sccm, the flow rate of N2 is 6000sccm, the flow rate of H2 is 7200sccm, the discharge power of the PECVD equipment is 13KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 50ms, and the process time of the PECVD equipment is 0.5H.

[0192] in, Figure 7A-7C In the figure, the EDS characterization diagrams of each thin film material were tested at two points on the sample of the film.

[0193] Among them, Fig. 7A From the EDS characterization diagram shown, it can be seen that in the formed film, the weight proportions of Si elements tested at two points are 96wt% and 94.36wt% respectively, the weight proportions of C elements are 3.8wt% and 5.4wt% respectively, and the weight proportions of O elements are 0.3wt%.

[0194] Among them, Figure 7B From the EDS characterization diagram shown, it can be seen that in the formed film, the weight proportion of Si element at the two test points is 91.7wt% and 91.2wt%, the weight proportion of N element is 4.6wt% and 4.3wt%, the weight proportion of C element is 3.5wt% and 4.4wt%, and the weight proportion of O element is 0.1wt%.

[0195] in, Figure 7C The scales of the horizontal axes of the upper and lower EDS characterization graphs are different. Figure 7C From the EDS characterization diagram shown, it can be seen that in the formed film, the weight proportion of Si element at the two test points is 91.0wt% and 91.8wt%, the weight proportion of N element is 4.4wt% and 4.3wt%, the weight proportion of C element is 4.4wt% and 3.7wt%, and the weight proportion of O element is 0.2wt%.

[0196] See also Figure 8 , Figure 8 XRD patterns of different films provided in this application.

[0197] Among them, XRD (X-Ray Diffraction) is a technology used to study the atomic arrangement structure inside solid materials. It is based on the diffraction phenomenon that occurs when X-rays interact with matter and can provide detailed information about the crystal structure of the material.

[0198] It should be noted that Figure 8 In the XRD diagram shown in , the XRD ordinates of each sample are different, and only the differences in the positions of the 10-70 diffraction peaks are evaluated by comparison with the same diagram.

[0199] Among them, the preparation conditions of the film characterized by the XRD pattern shown in SP1 are: a reaction gas composed of SiH4 and H2 is introduced into the reaction chamber, the temperature of the reaction chamber is 440°C, the pressure of the reaction chamber is 410Pa, the flow rate of SiH4 is 4300sccm, the flow rate of H2 is 9600sccm, the discharge power of the PECVD equipment is 13KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 50ms, and the process time of the PECVD equipment is 0.5H.

[0200] The film formed after the above process is an intrinsic silicon film, that is, the XRD pattern of the intrinsic silicon film characterized by SP1.

[0201] Among them, the preparation conditions of the film characterized by the XRD pattern shown in SP2 are: a reaction gas composed of SiH4 and SiN3 is introduced into the reaction chamber, the temperature of the reaction chamber is 440°C, the pressure of the reaction chamber is 410Pa, the flow rate of SiH4 is 2200sccm, the flow rate of SiN3 is 15000sccm, the discharge power of the PECVD equipment is 13KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 50ms, and the process time of the PECVD equipment is 0.5H.

[0202] The film formed after the above process is a silicon nitride film, that is, the XRD pattern of the silicon nitride film characterized by SP2.

[0203] Among them, the preparation conditions of the film characterized by the XRD pattern shown in SP3 are: a reaction gas composed of SiH4, SiN3, H2, and N2 is introduced into the reaction chamber, the temperature of the reaction chamber is 440°C, the pressure of the reaction chamber is 410Pa, the flow rate of SiH4 is 4300sccm, the flow rate of SiN3 is 8000sccm, the flow rate of H2 is 7200sccm, the flow rate of N2 is 6000sccm, the discharge power of the PECVD equipment is 13KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 50ms, and the process time of the PECVD equipment is 0.5H.

[0204] The film formed after the above process is a composite film of a silicon nitride film and an intrinsic silicon film, that is, SP3 characterizes the XRD pattern of the composite film of the silicon nitride film and the intrinsic silicon film.

[0205] Among them, the preparation conditions of the film characterized by the XRD pattern shown in SP4 are: a reaction gas composed of SiH4, N2 and H2 is introduced into the reaction chamber, the temperature of the reaction chamber is 440°C, the pressure of the reaction chamber is 410Pa, the flow rate of SiH4 is 4300sccm, the flow rate of N2 is 6000sccm, the flow rate of H2 is 7200sccm, the discharge power of the PECVD equipment is 13KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 50ms, and the process time of the PECVD equipment is 0.5H.

[0206] The thin film formed after the above process is Si x N y Poly-Si z :H film, namely SP4 characterization of Si x N y Poly-Si z :XRD pattern of H film.

[0207] Among them, the preparation conditions of the film characterized by the XRD pattern shown in SP5 are: a reaction gas composed of SiH4 and N2 is introduced into the reaction chamber, the temperature of the reaction chamber is 440°C, the pressure of the reaction chamber is 410Pa, the flow rate of SiH4 is 4300sccm, the flow rate of N2 is 12000sccm, the discharge power of the PECVD equipment is 13KW, the duty cycle of the RF power supply of the PECVD equipment is 4 / 50ms, and the process time of the PECVD equipment is 0.5H.

[0208] The thin film formed after the above process is Si x N y Poly-Si z Thin film, namely SP5 characterization Si x N y Poly-Si z XRD patterns of the films.

[0209] Depend on Figure 8 It can be seen that in the XRD pattern of the intrinsic silicon film in SP1, there is a peak at 27±, which can be judged that amorphous silicon is converted into polycrystalline silicon after crystallization at high temperature (910℃), and the diffraction peak is sharp, indicating a high content. Correspondingly, the other samples have no peak at this position, that is, it can be judged that there is no single crystal silicon in the structure of the other samples.

[0210] In the XRD pattern of the silicon nitride film in SP2, a bulging state (typical amorphous state) is shown at 30± and there is no SIN crystallization-related peak in the XRD.

[0211] In the XRD diagram of the composite film of the silicon nitride film and the intrinsic silicon film in SP3, the curve is similar to the XRD diagram of the silicon nitride film, that is, the amorphous silicon film layer cannot be crystallized normally even after being subjected to a high-temperature crystallization environment under the influence of the SiNx structure.

[0212] Si in SP4 x N y Poly-Si z :XRD patterns of H films and Si in SP5 x N y Poly-Si z The XRD graph of the film is quite different from the curve of the XRD graph of the silicon nitride film in SP2. And the material structure of the material grown by SP4 and SP5 is quite different from the material structure state of the material grown by SP3.

[0213] The above description is only an implementation method of the present application, and does not limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly used in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A thin film material, characterized in that: Including Si x N y Poly-Si z Thin film and / or Si x N y Poly-Si z :H film; and the mass of the Si element and the N element in the thin film material, the ratio of the total mass of all elements contained in the thin film material is less than or equal to 100wt%.

2. The film material according to claim 1, characterized in that: include: The Si stacking arrangement x N y Poly-Si z Thin films and a-Si:H thin films; or The Si stacking arrangement x N y Poly-Si z :H film and a-Si:H film.

3. The thin film material according to claim 1, characterized in that: include: The Si stacking arrangement x N y Poly-Si z Thin film, the Si x N y Poly-Si z :H film and a-Si:H film.

4. The thin film material according to claim 1, characterized in that: The thickness of the thin film material is 5nm-6μm.

5. A method for preparing a thin film material, characterized in that: include: placing a growth substrate in the reaction chamber; A reaction gas is introduced into the reaction chamber and ionized into plasma by radio frequency discharge, wherein the reaction gas includes SiH4 and N2.

6. The method for preparing a thin film material according to claim 5, characterized in that: In the step of introducing reaction gas into the reaction chamber, the reaction gas consists of SiH4 and N2.

7. The method for preparing a thin film material according to claim 5, characterized in that: In the step of introducing reaction gas into the reaction chamber, the reaction gas consists of SiH4, N2 and H2.

8. The method for preparing a thin film material according to claim 5 or 7, characterized in that: The step of introducing a reaction gas into the reaction chamber and ionizing plasma by radio frequency discharge specifically includes any two of the following three steps: A first reaction gas is introduced into the reaction chamber, and a first plasma is ionized by radio frequency discharge; the first reaction gas is composed of SiH4 and N2; A second reaction gas is introduced into the reaction chamber, and a second plasma is ionized by radio frequency discharge; the second reaction gas is composed of SiH4, N2 and H2; A third reaction gas is introduced into the reaction chamber, and a third plasma is ionized by radio frequency discharge; the third reaction gas is composed of SiH4 and H2.

9. The method for preparing a thin film material according to claim 5 or 7, characterized in that: The step of introducing a reaction gas into the reaction chamber and ionizing the plasma by radio frequency discharge specifically includes the following three steps: A first reaction gas is introduced into the reaction chamber, and a first plasma is ionized by radio frequency discharge; the first reaction gas is composed of SiH4 and N2; A second reaction gas is introduced into the reaction chamber, and a second plasma is ionized by radio frequency discharge; the second reaction gas is composed of SiH4, N2 and H2; A third reaction gas is introduced into the reaction chamber, and a third plasma is ionized by radio frequency discharge; the third reaction gas is composed of SiH4 and H2.

10. The method for preparing a thin film material according to claim 5 or 6, characterized in that: The method is carried out using PECVD equipment; wherein, The temperature of the reaction chamber is 350-480°C; The pressure of the reaction chamber is 400-500Pa; The flow rate of SiH4 is 500-10000sccm; The flow rate of N2 is 1000-20000sccm; The discharge power of the PECVD equipment is 0-40KW; The duty cycle of the radio frequency power supply of the PECVD device: 0-100 / 1-1000ms; The process time of the PECVD equipment is 0-10H.

11. The method for preparing a thin film material according to any one of claims 7 to 9, characterized in that: The method is carried out using PECVD equipment; wherein, The temperature of the reaction chamber is 300-480°C; The pressure of the reaction chamber is 250-600 Pa; The flow rate of SiH4 is 500-10000sccm; The flow rate of N2 is 1000-20000sccm; The flow rate of H2 is 1000-20000sccm; The discharge power of the PECVD equipment is 0-40KW; The duty cycle of the radio frequency power supply of the PECVD device: 0-100 / 1-1000ms; The process time of the PECVD equipment is 0-10H.

12. A method for manufacturing a graphite boat carrier, characterized in that: include: A thin film is deposited on a graphite boat using the method for preparing a thin film material according to any one of claims 5 to 11.

13. A graphite boat carrier, characterized in that: include: Graphite boat; An isolation film, covering the surface of the graphite boat; Wherein, the isolation film is a film material as described in any one of claims 1-4; or the isolation film is a film material deposited on the graphite boat by using the preparation method as described in any one of claims 5-11.

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