TWI345595B - Nh3 plasma treating method for forming poly-crystalline - Google Patents

Description

1345595 IX. Description of the invention: [Technical field to which the invention pertains] This invention refers to a method for treating ammonia plasma which forms polycrystalline germanium, and more particularly to an ammonia plasma processing method for forming polycrystalline germanium in a semiconductor process. [Prior Art]

For today's flat panel display industry, amorphous germanium thin film transistors are widely used in common flat panel displays, and low temperature process (LTP) polycrystalline silicon (poly-silicon) thin film transistors. (Thin Film Transistor, TFT) is widely used in large area display electronics such as Active Matrix Liquid Crystal Sisplays (AMLCDs) and Active Organic Electroluminescent Display (Active Matrix) Organic Light Emitting Displays, AMOLEDs). However, since the low-temperature polycrystalline slab thin film transistor has a higher driving current than the conventional amorphous silicon wafer (am-rph〇US silicon, a-Si) thin film transistor, and for the n-type and P-type channels The TFT is easy to manufacture and the like, so that the complementary metal oxide semiconductor (CMOS) and its peripheral drivers can be effectively integrated in the same substrate, so the external connection of the CM〇s (extemal) The number of connections will be effectively reduced, which will increase the reliability of CM〇s related products and reduce manufacturing costs. Therefore, research related to polycrystalline germanium is one of the key research and development aspects of the flat panel display industry. The process of forming polycrystalline germanium is roughly as follows: depositing a layer of amorphous phase film' and then undergoing a crystallization process to become a large-grain having a low density of 5 1345595 low grain-boundary density. Polycrystalline germanium. There are many techniques for crystallizing amorphous germanium into large-grain polycrystalline germanium, such as: s〇lid Phase Crystallization 'SPC, excimer iaser crystallization, and electron beam induced crystallization (electr) 〇n_beam_indueed crystallization). The SPC method places the film at a high temperature (6 〇〇 in a crucible oven for a fixed time (usually 20 to 60 hours) annealing treatment (31111 Qiu 1_) for crystallization, due to simple operation and low cost, and has a smooth surface. The ability and the film produced by the SPC method have a high degree of reproducibility and are widely used, but the SPC method must be maintained at 600. (The temperature is about 20 to 60 hours to ensure the production of polycrystalline germanium film with large particles. Therefore, spc is not conducive to commercial production and manufacturing. Therefore, many improved methods for shortening the crystallization time of the spc method have been proposed, such as metal_indueed crystallization, germanium-induced crystallization, and crystallization. Pre-plasma treatment before crystallization, etc., wherein the pre-crystallization plasma treatment method can effectively reduce the crystallization time to 4 hours in an environment of 600. Others such as hydrogenation (hydr〇genati〇n) The method is also proposed to reduce the energy level of polycrystalline germanium to improve the performance of the polycrystalline germanium constituent elements. = The formation of polycrystalline germanium structures by the above methods requires more consumption. The crystallization time (12~24 hours)' and the weak Si-H bond in the formed polycrystalline germanium structure make the overall structure unreliable. The job is due to the lack of the prior art. After careful research on bribery, and the spirit of reluctance, I finally conceived the book, "the method of treating ammonia in the process of forming polycrystalline dreams", which can overcome the weak hydrogen bonding and long crystallization in the conventional polycrystalline germanium structure technology. The defect of time, etc., is a brief description of the case. The present invention is based on high density Density asma - Chemical Vapor Deposition (HDP-CVD) ^AA^ » In ammonia «, the phase-by-molecular heat source holds, and the carbon-emitting amorphous stone structure is at least 3 minutes, in order to carry out the ammonia electricity gathering, and the compound structure is usually obtained. The annealing process first performs ammonia electropolymerization on the amorphous heterostructure, so the ammonia plasma treatment is also called pretreatment. After the pretreatment, the conversion of the amorphous stone structure to the polycrystalline stone can be significantly reduced. Structure required knot (this (four) 2 to 12 hours , f know the technology 12~24 hours)' and the hydrogen radicals generated by the pre-treated amorphous stone structure can help form the polycrystalline sprite, and at the same time, the pretreatment can also form a strong Si-N bonding to replace the weaker bonding bond or SA bonding, so that it can be further improved - the thermal carrier effect of the transistor (4) earner effect) 'to improve the electrical properties of the transistor component And reliability. According to the concept of the present invention, an ammonia electropolymerization treatment method for forming polycrystalline spine is proposed, which comprises the steps of forming an amorphous hetero-base layer; exposing the amorphous rock to the milk electric ferry; projecting the excimer mine Shooting on the amorphous stone; and annealing the amorphous germanium to form a polycrystalline stone. Preferably, the lion is a polycrystalline egg ammonia plasma treatment method provided by the present invention, wherein the base layer is a buffer oxide layer.车乂佳地'The present invention provides a method for forming a polycrystalline ammonia electropolymerization process. The ammonia system is formed by pure Wei, which is exposed to the ammonia via a gamma chemical vapor deposition (CVD) process. Among the plasmas, the chemical phase deposition process is - electron resonance resonance Peicheng CR-CVD), a plasma-assisted chemical vapor deposition (PECVD) process or a high-density plasma chemical vapor deposition ( HDP-CVD) process. Preferably, the present invention provides a method for treating a polycrystalline silicon-forming ammonia plasma, wherein the ammonia plasma is a plasma having a density greater than 10"ions/m3. Preferably, the polycrystalline germanium is formed by the present invention. The ammonia plasma treatment method 'when the exposure step is performed, the temperature of the substrate is maintained at 300 〇 C. Preferably, the present invention provides the polycrystalline hydrazine-forming ammonia plasma treatment method, wherein the exposure step is performed The RF power density is set to 〇.6 W/cm 2 〇 preferably the present invention provides a method for treating a polycrystalline ruthenium ammonia slurry, wherein the exposure step lasts for at least 30 minutes. Preferably, the present invention provides The ammonia plasma treatment method for forming polycrystalline germanium 'where the annealing step is applied by a solid phase crystallization method, a quasi-molecular laser crystallization method, an electron beam induction crystallization method, a furnace tube annealing or a laser annealing. The invention provides a method for treating a polycrystalline petrochemical ammonia slurry, comprising the steps of: forming an amorphous germanium on a substrate; treating the amorphous germanium with ammonia; and annealing the non- Preferably, the present invention provides a method for treating a polycrystalline strontium-containing ammonia plasma, wherein the ammonia plasma treatment step further comprises the steps of: exposing the amorphous sand to an ammonia plasma; and projecting an excimer The invention is characterized in that the substrate is a buffer oxide layer. Preferably, the polycrystalline germanium is provided by the present invention. Ammonia plasma __ method γ, wherein the ammonia electricity is formed by pure ammonia gas, the amorphous stone is deposited by the f chemical emulsion deposition (CVD) process (4) exposed to the Wei plasma, the chemical 5 / s is - electron cyclotron resonance chemical vapor deposition (ecr_cvd) 'long, - electric auxiliary chemical vapor deposition (PECVD) process or a high density plasma chemical vapor deposition (hdp_cvd) process. The method for forming a polycrystalline ruthenium ammonia slurry according to the present invention, wherein the gas plasma is a plasma having a density of more than 10, ions/m3. Preferably, the polycrystalline strontium-forming ammonia plasma provided by the present invention is provided. Method, where the exposure is performed In the step, the temperature of the substrate is maintained at 3 (nine) C. Preferably, the method for treating a polycrystalline silicon-forming ammonia plasma provided by the present invention, wherein the exposure step is performed, the RF power density is set to 〇.6 W/cm 2 °. Preferably, the method for treating a polycrystalline silicon-forming ammonia plasma provided by the present invention, wherein the exposing step is continued for at least 3 minutes. Preferably, the present invention provides the polycrystalline silicon-forming ammonia plasma processing method, wherein The annealing step is applied by a solid phase crystallization method, a quasi-molecular laser crystallization method, an electron beam induced crystallization method, a furnace tube annealing or a laser annealing. [Embodiment] This case will be explained by the following implementation case. Fully understood, so that people who are skilled in the art can do it, but the implementation of this case is not 1345595. The following examples can be used to limit their implementation.

Hereinafter, the method for treating polycrystalline germanium-forming ammonia plasma proposed by the present invention is used in the process of low-temperature polycrystalline germanium film transistor (LTP poly-Si TFT) as an example, and the description of the embodiments of the present invention is carried out. Referring to the first figure, a flow chart of the implementation steps of the polycrystalline germanium-forming ammonia plasma treatment used in the LTP P〇ly-SiTFT process proposed in the present invention is shown. The first figure shows an LTP poly-Si TFT being fabricated, which is a self-aligned N-channel TFT 'which includes: substrate 1 缓冲, buffer oxide layer 11, amorphous 矽The layer 12, the polysilicon layer 13, the gate dielectric layer 14, the active layer 15, the polysilicon gate 16 and the ammonia (NH3) plasma 17, wherein the substrate 10 can be a generally common germanium substrate. In carrying out the method disclosed in the present invention, a substrate 1 is first provided, and a layer-up buffer oxide layer 11 is deposited over the substrate 10. Next, using the Electro-Assisted Chemical Vapor Deposition System (Plasma Enhanced)

Chemical Vapor Deposition (PECVD) was combined with pure SiH4 as the reaction gas' environmental variable at a reaction temperature of 250. (:, the pressure is

500 mTorr (lTorr = 133.3 Pa), and an RF power density of 〇.25 W/cm2, to deposit a layer of amorphous germanium layer 12 composed of Si:H having a thickness of 115 nm over the buffer oxide layer 11 as a later ammonia gas The precursor layer of the slurry treatment. Then use high-density plasma (referred to as plasma density of 10"ions / m3 plasma 'High Density Plasma, HDP' chemical vapor deposition (CVD) system and pure ammonia gas (ΝΗχ) as the reaction plasma, The amorphous ruthenium layer 12 is subjected to ammonia plasma treatment. The amorphous slab layer 12 is first exposed to the ammonia plasma, wherein the environmental variable is set to a substrate temperature of 300 ° C and an RF power density of

Cinstallization takes about 2 to 12 hours. Take the active layer 15. A layer of 12 〇nm (individual active device) is deposited in two layers to serve as a HDP-CVD method 'tetraethyl orthosilicate oxide (TEOS/Cy layer) over the active layer 15 As the gate dielectric layer 14. The above-mentioned ammonia electropolymerization treatment and annealing treatment are repeated to form a _ layer polycrystalline layer above the gate dielectric layer 14 as a polycrystalline (tetra) pole 16. Reuse of reactive ion dry etching Reactive i〇n dry etching to form a gate electrode (not shown in the figure). Further, phosphorus (10) sinking (10) is used as a dopant to reuse self-aligned P+ ion implantation. (i〇n implantation) method, the source, the drain and the gate were formed at an implant dose of 5xl015cm2 (all are not shown in the figure). The ionized dopant region is then activated at an energy density of 2 〇〇 mJ/cm 2 at room temperature using an excimer laser annealing procedure. A 500 nm thick layer of hdp-cvd TE0S ruthenium oxide xide) was deposited in an environment of 300 ° C (not shown). Finally, contact holes (not shown in the figure) were formed at appropriate positions, and electrodes (not shown) were formed to complete the fabrication of the LTP P〇ly-Si TFT. In the above-mentioned process, the polycrystalline germanium layer 1J is formed by annealing treatment, and the amorphous austenite layer as the lead layer is subjected to ammonia plasma treatment, and the amorphous germanium layer 12 can be significantly reduced by the ammonia plasma treatment. The crystallization time required for conversion to the polysilicon layer 13 and the hydrogen radicals generated by the pretreated amorphous germanium layer can help form polycrystalline germanium seeds, and the use of this pretreatment can also form strong Si-N bonds. In order to replace the more fragile si_H bond or Si-Si bond, the carrier effect of the transistor can be further improved to improve the electrical and reliability of the transistor component. Please continue to refer to the second figure, which is the implementation side of the ammonia plasma processing method for forming polycrystalline germanium. The above part of the ammonia electrolysis can be integrated as follows: Step 1. Exposing the amorphous layer 12 to the ammonia slurry 17; Step 2: projecting the excimer laser onto the amorphous layer 12 for 30 minutes ;as well as. Step 3: using the SPC method for 4 to 12 hours to at least 600 C annealing the non-00 layer 12, converting the amorphous layer to the polycrystalline layer above the step - and the second step may be collectively referred to as ammonia slurry pre- Pretreatment. The three steps disclosed above are as shown in the second figure. The above is only the preferred embodiment of the present invention, and the details of the implementation of (4) cannot be limited. This case has to be modified by the philosophers of the literary arts, and they are all like the (4) ritual protectors. That is to say, the big test (4) ψ 专 专 专 专 骑 骑 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a flow chart of the implementation steps of the process for forming polycrystalline germanium in the plasma processing of LTP poly-SiTFT proposed by the present invention; and the second figure is the ammonia lamp forming polycrystalline germanium in the present invention. Flow chart of the implementation steps of the slurry processing method. [Main component symbol description]

10 : substrate 12 : amorphous germanium layer 14 · gate oxide layer 16 : polysilicon gate 11 : buffer oxide layer 13 : polysilicon layer 15 : active layer 17 : ammonia plasma

e 13

Claims (1)

_, the scope of the patent application: the in--a semi-conductive crystal guide comprising a (4) coffee material component on a non-base layer to form the amorphous germanium layer; exposing the amorphous rock layer to the ammonia electropolymer; A molecular laser is irradiated on the amorphous layer; and the amorphous layer is annealed to form a polycrystalline layer. The method described in the 1st item “shoots the semiconductor pre-order and becomes the process of the segment (4), such as the marriage, FE0L) — the process ((4) yp Css), the front section of the solar panel. Wire-active matrix organic light-emitting diode _(10)D) The method described in the first aspect of the invention, wherein the base layer is -# 4 by the pure = ^ coffee 1st branch, its towel Wei plasma traitor and trace + ί '5 turn the secret through the chemical vapor deposition (CVD) system private exposure in the ammonia, The chemical vapor deposition process is a method of vapor deposition (ECR_CVD), a method of electro-chemical-assisted (four-degree) electro-chemical vapor deposition, L==r:』r, wherein the surface is the first item of the 6-bovine range. The method of the present invention, wherein the temperature of the substrate is maintained at 30 (rc. 14 steps, RF_=2=^f;, the exposure is performed. 8. For example, _ please patent Fanyuan first item# ^ Continue for at least 3G minutes. Financial method, shoot the exposure step 9. As described in the first paragraph of the patent application scope ### application-in-reduction method, the quasi-annealing step should be crystallization, a furnace, m 1. Japanese and Japanese law, an electron beam sensation, XJ Tamachi, . 'mouth-day-day method, one furnace tube annealing or - laser «SjI. 刖矽=- ammonia plasma treatment has not been made as component two Forming the amorphous dream on a base layer, 11. using the ammonia plasma to work on an amorphous dream; and annealing the amorphous rock to form a polycrystalline stone. The method described in the first paragraph of the 1G item The semiconductor two = ί: _ segment process (fine "cheek, dirty", segment process] other & array process (array pr〇cess), a solar panel front process. 2 silk matrix organic light-emitting diode "MOLED} front section The method of claim 1 , wherein the gas electropolymerization step further comprises the steps of: exposing the amorphous stone to the ammonia electricity; and discharging the cylinder excimer laser to the amorphous rock. Lai, wherein the base layer is H, as in the method of claim 10, wherein the oxygen 15 (==: ammonia-chemical vapor deposition f V * private Wei towel, the vapor deposition process is An electron-reducing chemical gas accumulation (ECR-CVD) process, an electropolymerization-assisted chemical vapor deposition (CVD) process, or a high-density electropolymerization chemical vapor deposition (HDP-CVD) process. The method of claim 1 or 12, wherein the ammonia plasma is an electric music having a density greater than 10"i〇ns/m3. 16. The method of claim 1G, wherein the exposing step is performed When the temperature of the substrate is maintained at 3 〇〇. · 17 · As described in claim 10 The method wherein the RF power density is set to 〇6w/cm2. 18. The method of claim 10, wherein the exposing step lasts for at least 30 minutes. The method of the present invention, wherein the annealing step is performed by a solid phase crystallization method, a quasi-molecular laser crystallization method, an electron beam induced crystallization method, a furnace tube annealing or a laser annealing.