A method of passivating a iii-v device and a passivation apparatus

Abstract

The application relates to the technical field of semiconductors, in particular to a III-V device passivation method and a passivation device, the III-V device passivation method comprising the following steps: providing a III-V device, the III-V device having a III-V material surface, and the III-V material surface having a natural oxide layer; placing the III-V device in a reaction chamber, introducing a reaction gas into the reaction chamber, the reaction gas reacting with the natural oxide layer to generate volatile products, and removing the natural oxide layer in a self-limiting manner; purging the reaction chamber to remove the volatile products and excess reaction gas; depositing an oxygen-free film on the III-V material surface in situ by using the reaction chamber, and forming an oxidation composite film on the surface of the oxygen-free film. The application at least has the advantages of solving the problems of incomplete removal of the oxidation layer, easy damage to the material surface, poor denseness of the passivation layer, high cost and low production efficiency in the III-V material passivation technology.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor technology, and particularly relates to a passivation method and passivation equipment for III-V group devices. Background Technology

[0002] Semiconductor III-V group materials, such as GaAs, InP, and GaN, occupy a pivotal position in today's technological field due to their superior optoelectronic properties. Taking high-frequency, high-speed microelectronic devices as an example, the rapid development of 5G and even future 6G communication technologies places higher demands on chip processing speed and signal transmission frequency. III-V group materials, due to their high electron mobility, can significantly enhance the speed of electron transport within the material, enabling chips to perform exceptionally well in high-frequency signal processing. This effectively reduces signal transmission delay and improves data processing efficiency, thereby meeting the high-performance chip requirements of devices such as 5G base stations and high-speed mobile terminals.

[0003] In the field of optoelectronic devices, III-V materials have also shone brightly. For example, in light-emitting diodes (LEDs), high-brightness, high-efficiency LEDs based on III-V materials are widely used in lighting and display backlighting. Taking gallium nitride (GaN)-based LEDs as an example, their luminous efficiency is far higher than traditional lighting sources, and they can achieve a narrower emission spectrum, resulting in more vivid and realistic colors in display backlighting. In laser diodes, III-V materials are widely used in fiber optic communication, laser printing, and optical storage. In fiber optic communication, III-V material laser diodes can generate high-power, narrow-linewidth laser beams, enabling long-distance, high-speed data transmission, significantly increasing the bandwidth and transmission distance of communication networks.

[0004] However, III-V group materials face severe challenges in practical applications. Their surfaces and sidewalls are extremely sensitive to oxygen and water in the environment, readily undergoing chemical reactions to form complex natural oxide layers. These natural oxide layers not only contain aluminum oxide but also encompass various oxides such as gallium oxide, indium oxide, and arsenic oxide. The presence of these oxide layers triggers a series of serious problems. From the perspective of surface state density, the formation of the oxide layer leads to a sharp increase in surface state density, with a large number of surface states becoming recombination centers for charge carriers, significantly shortening the carrier lifetime. In semiconductor devices, the shortened carrier lifetime directly affects device performance. For example, in transistors, it reduces switching speed and increases signal transmission distortion. From the perspective of device leakage current, the presence of the oxide layer disrupts the original electrical properties of the material, leading to increased leakage current. This not only increases device power consumption and reduces energy efficiency but can also cause device failure in severe cases, affecting the stability and reliability of the entire circuit system. In laser diodes, surface oxides form non-radiative recombination centers that absorb photons, generate heat, and cause catastrophic optical damage to the cavity surface, reducing the long-term performance and reliability of the laser diode and limiting its maximum output power.

[0005] Currently, passivation techniques for III-V group materials mainly include wet chemical processing, plasma treatment, chemical vapor deposition, and high-vacuum cleavage combined with molecular beam epitaxy. Wet chemical processing utilizes a chemical solution to react with the oxide layer on the material surface to remove the oxide layer. However, this method has many drawbacks in practice. On the one hand, it is difficult to precisely control the thickness of the oxide layer removed by the chemical solution, which can easily lead to over-etching or under-etching. This affects the flatness and integrity of the material surface, thus affecting the consistency of device performance. On the other hand, during wet chemical processing, impurity ions in the chemical solution are easily adsorbed onto the material surface, introducing new impurities. These impurities can alter the electrical properties of the material, increase carrier scattering, and reduce device mobility. Plasma treatment removes or passivates oxide layers by interacting with active particles in the plasma on the material surface. However, during the process, high-energy particles in the plasma bombard the material surface, causing sputtering and displacement of atoms and creating lattice defects. These defects become traps for charge carriers, affecting carrier transport, reducing device performance, and potentially accelerating material aging and failure. Traditional chemical vapor deposition (CVD) uses gaseous precursors to react chemically on the material surface, depositing a passivation film. However, the films deposited by this technique lack density, making it difficult to effectively prevent the intrusion of water and oxygen. Water and oxygen molecules can penetrate through the pores and defects of the film to the material surface, continuing to react with the material, resulting in poor passivation and an inability to maintain the long-term performance stability of the device. While high-vacuum cleavage combined with molecular beam epitaxy coating technology can grow high-quality epitaxial layers on material surfaces and achieve good passivation effects, this technology has extremely high equipment requirements, necessitating high-vacuum systems and precision molecular beam sources, resulting in high equipment purchase costs. Moreover, the process is complex, demanding on the operating environment and the technical skills of the operators, leading to extremely low production efficiency. Each coating process requires a significant amount of time and resources, keeping production costs high and severely limiting its application in large-scale industrial production. Summary of the Invention

[0006] In view of this, the present invention aims to provide a passivation method and passivation equipment for III-V group devices, which at least helps to solve the problems existing in the passivation technology of III-V group materials, such as incomplete removal of oxide layer, easy damage to material surface, poor density of passivation layer, high cost and low production efficiency.

[0007] To achieve the above objectives, the technical solution created by this invention is implemented as follows:

[0008] This invention provides a passivation method for a III-V group device, comprising: providing a III-V group device having a III-V group material surface with a native oxide layer; placing the III-V group device in a reaction chamber, introducing a reaction gas into the reaction chamber, the reaction gas reacting with the native oxide layer to generate volatile products, thereby removing the native oxide layer in a self-limiting manner; purging the reaction chamber to remove the volatile products and excess reaction gas; and depositing an oxygen-free thin film in situ on the III-V group material surface using the reaction chamber, followed by forming an oxide composite film on the surface of the oxygen-free thin film.

[0009] Furthermore, the natural oxide layer includes at least one of aluminum oxide, gallium oxide, indium oxide, and arsenic oxide.

[0010] Furthermore, the process temperature for introducing reactive gas into the reaction chamber to remove the natural oxide layer is in the range of 20℃ to 500℃; introducing reactive gas into the reaction chamber to remove the natural oxide layer includes: performing one round of reaction or performing multiple rounds of the same reaction. For performing multiple rounds of the same reaction, purging is performed between two rounds of reaction to remove volatile products and excess reactive gas generated in the previous round of reaction.

[0011] Furthermore, each round of reaction introduces one type of reactant gas or N different reactant gases; for each round of reaction introducing N different reactant gases, the N reactant gases are introduced sequentially. If n is defined as the sequence number of the reactant gases introduced, the (n+1)th reactant gas introduced is used to react with the non-volatile byproducts generated in the previous reaction to generate volatile products, or the (n+1)th reactant gas introduced is used to remove the remaining natural oxide layer that was not removed in the previous reaction.

[0012] Furthermore, for the introduction of a single reactant gas, the reactant gas includes one of the following: Cl2, CCl4, CHCl3, CH2Cl2, BCl3, HCl, NH4Cl, C5H9Cl, SiCl4, TiCl4, SbCl5, PCl3, InI3, Na2S2O3, H2S, (NH2)2CS, thiols, sulfonyl compounds, sulfonic acid compounds, sulfonate esters, sulfonamides, thiocarboxylic acids and their derivatives, DMF, low-energy Ar plasma, low-energy N plasma, and low-energy H plasma; for the introduction of N different reactant gases, the first introduced reactant gas includes CCl4, CHCl3, CH2Cl2, HCl, SiCl4, TiCl4, BCl3, HF, Hhfac, The reaction gases introduced each time, except for the first time, include one of the following: NF3, CF4, a mixture of CF4 and H2, SF6, NH4F, BF3, PF5, XeF2, CHF3, and NH4HF2. Other than the first introduction, the remaining reaction gases introduced each time include one of the following: low-energy Ar plasma, low-energy H plasma, DMAC, TMA, Sn(acac)2, H2S, InI3, carbonyl sulfide, (NH2)2CS, Ga(NMe2)3, trimethyl borate, Al(NMe2)3, TMGa, TEGa, TMI, DMZn, thiols, thioethers, sulfonyl compounds, sulfonamides, thiocarboxylic acids and their derivatives, BTBAS, and ZDEC. Here, "low-energy" refers to energy less than a preset value, which is in the range of 20 eV to 30 eV.

[0013] Furthermore, before forming an oxygen-free film after removing the natural oxide layer, the process also includes: using atomic H, low-energy N plasma, or S-containing compounds to remove surface dangling bonds or surface states on the surface of III-V group materials to reduce the surface state density.

[0014] Furthermore, forming an oxygen-free thin film includes: depositing an oxygen-free thin film in situ on the surface of a III-V group material using a non-plasma-enhanced deposition process; forming an oxide composite thin film includes: forming an oxide composite thin film on the surface of the oxygen-free thin film using a plasma-enhanced atomic layer deposition process.

[0015] Furthermore, non-plasma-enhanced deposition processes include thermal atomic layer deposition processes.

[0016] Furthermore, materials for oxygen-free thin films include Li₂S, LiN₃, LiF, and LiAl. x F y 、LiAl x S y Lif-CF x BN, CoC x ErC2, FeC x、MoC x 、NbC x 、NiC x 、SiC、TaC x 、TiC x 、Toilet x 、HfAl x C y 、MoC x N y 、SiC x N y 、TaC x N y 、TiC x N y 、Toilet x N y 、TaAl x N y Cz、NaF、MgF2、MgTe、Al2S3、AlAs、AlF3、AlN、AlP、AlSb、Al:MoS2、AlGa x As y 、AlGa x N y 、AlW x F y 、CuAl x S y 、HfAl x C y 、InAl x N y 、RuAl x N y 、Sc x Heavy y F z 、TiAl x C y 、TiAl x N y 、AlIn x Ga y N z 、Si、CoSi2、NbSi、Si3N4、SiC、TaSi x 、Russian x N y 、SiC x N y 、WSi x N y 、AlP、CoP x 、GaP、InP、MoP、GaAs x P y 、Not x P yCuCl, PbCl2, PbBr x Cl y 、PbI x Cl y CaF2, CaS, CaSnS, SnCa x S y 、ScF3、ScN、Sc x To the y F z TiN TiC x TiS2, TiS3, CoTi x N y 、NbTi x N y 、RuTi x N y ,Tic x N y ,Thyme x N y 、TiV x N y 、VN、VS x 、TiV x N y 、VIn x S3y、MnAs、MnF2、MnS、MnTe、ZnMn x S y 、FeC x 、FeN x 、FeS x 、FeSe x 、Co3Sn2、Co x S y 、CoC x CoF2 CoN x 、CoP x 、CoS2、CoSe2、CoSi2、CoTi x N y 、FeCo x S y 、Ni2Ge、Ni3N、Ni3Sn2、NiC x NiF2 NiS x NiSe2 PtNi x Cu3N, CuCl, CuMn x 、CuSe x 、CuS x Cu:ZnS x 、CuAl x S y 、CuGa x S y 、CuInx S y CuSb x S y CuSn x S y CuZn x S y CuZn x Sn y S z FeZn x 、Zn3N2、ZnF2、ZnS、ZnSe、ZnTe、ZnIn x S y ZnMn x S y ZnSn x S y ZnS x Se y CdZn x Ga y S z 、GaAs、GaN、GaP、GaSb、GaS x CuGa x S y GaAs x P y GaIn x P y InGa x As y InGa x N y AlIn x Ga y N z CdZn x Ga y S z GeS, GeSb, GeSe, GeS x Gete x Ni2Ge, GeSb x Te y GeS x Se y Gete x S y GeSb x Se y Te z As2S3, InAs, MnAs, PbBr2, PbBr x Cl y PbBr x I y SrF2, SrS, SrCe x Sy 、SrS x Se y 、SrTb x S y YF3, ZrF4, ZrN x ZrS2, NbC x NbN, NbSi, NbTi x N y MoC x MoN x , MoP, MoS2, MoSe2, MoTe2, Al:MoS2, MoC x N y TiMo x N y RuPt x RuTa x N y RuTi x N y CdS, CdSe, CdTe, CdSe x Te y CdZn x S y CdZn x Ga y S z ,In2S3,In2Se3,InN,InSb,InSe,SnI2,SnN x SnSe x SnS x , SnTe, CaSnS, CsSnI3, Sb2S3, Sb2Se3, Sb2Te3, SbSe x Te y , CsI, PbI2, CsPbI3, BaS, HfF4, HfN x HfS2 and HfAl x C y At least one of the following; the oxidized composite film includes stacked Al2O3 layers and SiO2 layers; the thickness of the oxidized composite film is greater than the thickness of the oxygen-free film.

[0017] Another aspect of this invention provides a passivation device for III-V group devices, used to implement the passivation method for the aforementioned III-V group devices. The passivation device for III-V group devices includes: a reaction chamber, a surface oxide removal gas source, a surface passivation layer deposition gas source, an inert gas purging gas source, a vacuum pump system, a control system, and an exhaust gas treatment module. The surface oxide removal gas source, the surface passivation layer deposition gas source, the inert gas purging gas source, the vacuum pump system, and the exhaust gas treatment module are all connected to the reaction chamber. The control system is used to control the surface oxide removal gas source, the surface passivation layer deposition gas source, the inert gas purging gas source, the vacuum pump system, and the exhaust gas treatment module. The reaction chamber has a temperature-controllable heating module, a remote plasma module, and a gas spraying module.

[0018] Compared with the prior art, the present invention can achieve the following beneficial effects: The passivation method for III-V devices provided by the present invention is used to passivate the sidewalls of III-V materials in III-V devices. By introducing a reaction gas into the reaction chamber where the III-V device is placed, the reaction gas reacts with the self-limiting reaction of the native oxide layer to convert the native oxide layer on the surface of the III-V material into volatile products, thereby removing the native oxide layer on the surface of the III-V material in a self-limiting manner, avoiding incomplete removal of the native oxide layer and damage to the surface of the III-V material; after removing the native oxide layer, the same reaction chamber is used again under anaerobic conditions to first form an oxygen-free thin film in situ on the surface of the III-V material to form a preliminary oxygen-free film on the surface of the III-V material. For water and oxygen isolation, since the stability of oxygen-free films is relatively poor compared to oxygen-containing films, a high-density and high-stability oxide composite film is further formed in situ on the oxygen-free film to further improve the water and oxygen isolation effect. All passivation steps are completed in the same chamber. By changing the gas introduced and introducing the purging process, the reactions do not affect each other. The in-situ process does not introduce secondary oxidation due to changing chambers, ensuring a better passivation effect. Moreover, the entire passivation process will not cause bombardment damage to the material surface to introduce point defects, nor will it introduce chemical damage to affect the flatness. It does not require the use of high vacuum cleavage and molecular beam epitaxial coating, reducing costs and improving production efficiency. It realizes the precise removal of multiple oxide layers on the surface of III-V group materials and the in-situ deposition of high-quality passivation layers. Attached Figure Description

[0019] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments and descriptions of the invention are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0020] Figure 1 A schematic flowchart of the passivation method for III-V group devices described in the embodiments of the present invention;

[0021] Figure 2 This is a schematic diagram showing the connection relationship of various components in the passivation device for the III-V group devices described in the embodiments of the present invention. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not constitute a limitation thereof.

[0023] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other.

[0024] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," and "counterclockwise," etc., indicating orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this invention. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, features defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0025] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art will understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0026] The invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0027] refer to Figure 1This invention provides a passivation method for III-V group devices, comprising: providing a III-V group device having a III-V group material surface with a native oxide layer; placing the III-V group device in a reaction chamber, introducing a reaction gas into the reaction chamber, the reaction gas reacting with the native oxide layer to generate volatile products, thereby removing the native oxide layer in a self-limiting manner; purging the reaction chamber to remove the volatile products and excess reaction gas; depositing an oxygen-free thin film in situ on the III-V group material surface using the reaction chamber, and then forming an oxide composite film on the surface of the oxygen-free thin film. The oxygen-free thin film and the oxide composite film work synergistically to form a passivation layer, which is beneficial for further improving the waterproof and oxygen-barrier performance of the passivation layer.

[0028] In some examples, the III-V device can be a semiconductor laser, and the III-V material surface can be the exposed III-V material surface of the sidewall of the semiconductor laser.

[0029] Furthermore, the natural oxide layer includes at least one of aluminum oxide, gallium oxide, indium oxide, and arsenic oxide.

[0030] Furthermore, the process temperature for introducing reactive gas into the reaction chamber to remove the natural oxide layer is in the range of 10℃ to 500℃; introducing reactive gas into the reaction chamber to remove the natural oxide layer includes: performing one round of reaction or performing multiple rounds of the same reaction. For performing multiple rounds of the same reaction, purging is performed between two rounds of reaction to remove volatile products and excess reactive gas generated in the previous round of reaction.

[0031] In some embodiments, the reactant gases include: Cl2, CCl4, CHCl3, CH2Cl2, BCl3, CF4, HF, Hhfac, NF3, CF4, SF6, NH4F, BF3, PF5, XeF2, DMF, DMAC, CHF3, NH4HF3, TMA, a mixture of CF4 and H2, Sn(acac)2, HCl, NH4Cl, C5H9Cl, SiCl4, TiCl4, SbCl5, PCl3, SbCl5, PCl3, InI3, Na2S2O3, TEA, TMGa, TEGa, TMIn, and DM. At least one of Zn, DEZn, Acac, Glyme, low-energy Ar plasma, low-energy N plasma, low-energy H plasma, H2S, S, CS2, H2, carbonyl sulfide, (NH2)2CS thiourea, Ga(NMe2)3, thiols, thioethers, sulfonyl compounds, sulfonic acid compounds, sulfonate compounds, sulfonamide compounds, thiocarboxylic acids and their derivatives, BTBAS, trimethyl borate, Al(NMe2)3, ZDEC, acetylacetone, and ascorbic acid; wherein, low energy refers to energy less than a preset value, and the preset value is in the range of 20 eV to 30 eV.

[0032] Furthermore, each round of reaction introduces one type of reactant gas or N different reactant gases. For each round of reaction introducing N different reactant gases, the N reactant gases are introduced sequentially. If n is defined as the sequence number of the reactant gases, n+1 = 2, 3, ..., N-1 or N. The (n+1)th reactant gas introduced is used to react with the non-volatile byproducts generated in the previous reaction to generate volatile products, or the (n+1)th reactant gas introduced is used to remove the remaining natural oxide layer that was not removed in the previous reaction.

[0033] Furthermore, the introduced reaction gas includes one of the following: Cl2, CCl4, CHCl3, CH2Cl2, BCl3, HCl, NH4Cl, C5H9Cl, SiCl4, TiCl4, SbCl5, PCl3, InI3, Na2S2O3, H2S, (NH2)2CS, thiols, sulfonyl compounds, sulfonic acid compounds, sulfonate esters, sulfonamides, thiocarboxylic acids and their derivatives, DMF, low-energy Ar plasma, low-energy N plasma, and low-energy H plasma. "Low energy" refers to an energy lower than a preset value, which is in the range of 20 eV to 30 eV.

[0034] Furthermore, for the introduction of N different reactant gases, the first introduced reactant gas includes one of the following: CCl4, CHCl3, CH2Cl2, HCl, SiCl4, TiCl4, BCl3, HF, Hhfac, NF3, CF4, a mixture of CF4 and H2, SF6, NH4F, BF3, PF5, XeF2, CHF3, and NH4HF2. Except for the first introduction, the remaining reactant gases introduced each time include low-energy gases (energy < 20 eV to 30 eV). Ar plasma, low-energy (energy <20eV~30eV) H plasma, DMAC, TMA, Sn(acac)2, H2S, InI3, carbonyl sulfide, (NH2)2CS, Ga(NMe2)3, trimethyl borate, Al(NMe2)3, TMGa, TEGa, TMIn, DMZn, thiols, thioethers, sulfonyl compounds, sulfonamides, thiocarboxylic acids and their derivatives, BTBAS and ZDEC.

[0035] Understandably, if the composition of the natural oxide layer is relatively simple and a single reactive gas can remove it, then there is no need to introduce other reactive gases. However, if the composition of the natural oxide layer is more complex, other reactive gases can be introduced to react with the non-volatile byproducts formed in the previous step or components that could not be removed in the previous step, until both the natural oxide layer and non-volatile byproducts are converted into volatile substances, which are then removed by purging. Multiple rounds of reactions are performed to avoid generating too many volatile products that would halt the reaction. Furthermore, purging is necessary after each round of reaction because a significant amount of volatile products has already been generated in the reaction chamber, which is detrimental to the next round of reaction. Therefore, it is necessary to remove the volatile products generated in the previous round. In this way, not only alumina can be removed, but also oxides such as gallium oxide, indium oxide, or arsenic oxide can be removed incidentally. The entire process is self-limiting, preventing bombardment damage to the surface of III-V materials and avoiding chemical damage that could affect the surface smoothness.

[0036] It should be noted that N in this invention can be 2, 3, 4 or 5, depending on the composition of the natural oxide layer being removed.

[0037] In some embodiments, for each round of reaction, a reaction gas can be introduced into the reaction chamber simultaneously with H atoms.

[0038] Furthermore, before forming an oxygen-free thin film after removing the natural oxide layer, the process includes: thoroughly purging with high-purity N2 or Ar gas, and then, within the same reaction chamber, passivating the surface dangling bonds or surface states of the III-V group material surface using atomic H, low-energy N plasma, or S-containing compounds to further reduce the surface state density. Subsequently, after thorough purging with high-purity N2 or Ar gas again, an oxygen-free thin film is formed.

[0039] Furthermore, forming an oxygen-free thin film involves in-situ deposition of an oxygen-free thin film on the surface of a III-V material using a non-plasma-enhanced deposition process. This avoids bombardment damage to the surface of the III-V material.

[0040] Furthermore, non-plasma-enhanced deposition processes include thermal atomic layer deposition (TAL deposition). TLA deposition involves forming a thin film through the chemical adsorption and reaction of precursors on the material surface under specific temperature conditions.

[0041] Furthermore, the formation of the oxide composite film includes: forming an oxide composite film on the surface of an oxygen-free film using plasma-enhanced atomic layer deposition (PALD). PALD introduces plasma into the thermal atomic layer deposition process to form an oxide composite film with superior density and uniformity, thereby compensating for the shortcomings of oxygen-free films, such as low density and relatively poor stability. The oxide composite film formed using atomic layer deposition exhibits better uniformity and higher density, effectively preventing the intrusion of water and oxygen.

[0042] Furthermore, materials for oxygen-free thin films include Li₂S, LiN₃, LiF, and LiAl. x F y 、LiAl x S y Lif-CF x BN, CoC x ErC2, FeC x MoC x 、NbC x NiC x SiC, TaC x TiC x WC x HfAl x C y MoC x N y SiC x N y TaC x N y TiC x N y WC x N y、TaAl x N y Cz、NaF、MgF2、MgTe、Al2S3、AlAs、AlF3、AlN、AlP、AlSb、Al:MoS2、AlGa x As y 、AlGa x N y 、AlW x F y 、CuAl x S y 、HfAl x C y 、InAl x N y 、RuAl x N y 、Sc x Heavy y F z 、TiAl x C y 、TiAl x N y 、AlIn x Ga y N z 、Si、CoSi2、NbSi、Si3N4、SiC、TaSi x 、Russian x N y 、SiC x N y 、WSi x N y 、AlP、CoP x 、GaP、InP、MoP、GaAs x P y 、Not x P y 、CuCl、PbCl2、PbBr x Cl y 、PbI x Cl y 、CaF2、CaS、CaSnS、SnCa x S y 、ScF3、ScN、Sc x Heavy y F z 、TiN、TiC x 、TiS2、TiS3、CoTi x N y 、NbTi x N y 、RuTi x N y、TiC x N y 、TiMo x N y 、TiV x N y 、VN、VS x 、TiV x N y 、Vin x S3y、MnAs、MnF2、MnS、MnTe、ZnMn x S y 、FeC x 、FeN x 、FeS x 、FeSe x 、Co3Sn2、Co x S y 、CoC x 、CoF2、CoN x 、CoP x 、CoS2、CoCo2、CoSi2、CoTi x N y 、FeCo x S y 、Ni2Ge、Ni3N、Ni3Sn2、NiC x 、NiF2、NiS x 、NiSe2、PtNi x 、Cu3N、CuCl、CuMn x 、CuSe x 、CuS x 、Cu:ZnS x 、CuAl x S y 、CuGa x S y 、CuIn x S y 、CuSb x S y 、CuSn x S y 、CuZn x S y 、CuZn x Sn y S z 、FeZn x 、Zn3N2、ZnF2、ZnS、ZnSe、ZnTe、ZnIn x S y 、ZnMn x S y 、ZnSn x S y、ZnS x Claim y 、CdZn x Ga y S z 、GaAs、GaN、GaP、GaSb、GaS x 、CuGa x S y 、GaAs x P.S y 、GaIn x P.S y 、InGa x As y 、InGa x N y 、AlIn x Ga y N z 、CdZn x Ga y S z 、GeS、GeSb、GeSe、GeS x 、GeTe x 、Ni2Ge、GeSb x Until y 、GeS x Claim y 、GeTe x S y 、GeSb x Claim y Until z As2S3, InAs, MnAs, PbBr2, PbBr x Cl y 、PbBr x HE y SrF2, SrS, SrCe x S y 、SrS x Claim y 、SrTb x S y YF3, ZrF4, ZrN x 、ZrS2、NbC x 、NbN、NbSi、NbTi x N y 、MoC x 、MoN x MoP, MoS2, MoSe2, MoTe2, Al:MoS2, MoC x N y 、TiMo x N y 、RuPt x 、RuTax N y RuTi x N y CdS, CdSe, CdTe, CdSe x Te y CdZn x S y CdZn x Ga y S z ,In2S3,In2Se3,InN,InSb,InSe,SnI2,SnN x SnSe x SnS x , SnTe, CaSnS, CsSnI3, Sb2S3, Sb2Se3, Sb2Te3, SbSe x Te y , CsI, PbI2, CsPbI3, BaS, HfF4, HfN x HfS2 and HfAl x C y At least one of them, wherein the subscripts x and y of different materials may be the same or different, and the subscripts x and y depend on the valence state of the corresponding microparticles. As long as the valence state of the corresponding microparticles can be balanced to form a compound, the present invention does not limit it.

[0043] In some embodiments, the oxide composite film includes stacked Al2O3 layers and SiO2 layers; the thickness of the oxide composite film is greater than the thickness of the oxygen-free film.

[0044] In some embodiments, the thickness of the oxygen-free film is in the range of 1 nm to 50 nm. The thickness of the oxide composite film is in the range of 10 nm to 250 nm.

[0045] The following describes a specific embodiment of the passivation method for III-V group devices, using a III-V group device as an example of a semiconductor laser. The passivation method is as follows:

[0046] The cleaved semiconductor laser is placed in the reaction chamber, and high-purity N2 or Ar is used to repeatedly evacuate and purge the chamber to remove as much oxygen as possible.

[0047] Remove the natural oxide layer using the methods described above;

[0048] Use high-purity N2 or Ar to purge and remove all gaseous compound residues from the previous step;

[0049] Introducing atomic H, low-energy N plasma, or S-containing compounds can hydrogenate, nitridate, or sulfide the surface dangling bonds or surface states of III-V materials to passivate the surface of III-V materials and reduce the surface state density.

[0050] Use high-purity N2 or Ar to purge and remove all gaseous compound residues from the previous step;

[0051] An oxygen-free film is formed using the aforementioned method;

[0052] Use high-purity N2 or Ar to purge and remove all gaseous compound residues from the previous step;

[0053] An Al2O3 layer and a SiO2 layer were prepared sequentially using a plasma-enhanced atomic layer deposition process to form an oxide composite film, which further enhanced the water and oxygen barrier effect.

[0054] The passivation method for III-V group devices provided by this invention is carried out in situ, without the need for high vacuum cleavage and molecular beam epitaxy coating. This avoids contact between the device and the external environment during processing, reduces secondary pollution, and eliminates secondary oxidation introduced by changing the chamber. This ensures the stability and reliability of the passivation effect, while reducing production costs and improving production efficiency. Furthermore, the entire process does not cause bombardment damage to the material surface, thus avoiding point defects, nor does it introduce chemical damage that affects flatness.

[0055] refer to Figure 2 In another aspect, this invention provides a passivation device for III-V devices, used to implement the passivation method for the aforementioned III-V devices. The passivation device for III-V devices includes: a reaction chamber, a surface oxide removal gas source, a surface passivation layer deposition gas source, an inert gas purging gas source, a vacuum pump system, a control system, and an exhaust gas treatment module. The surface oxide removal gas source, the surface passivation layer deposition gas source, the inert gas purging gas source, the vacuum pump system, and the exhaust gas treatment module are all connected to the reaction chamber. The control system is used to control the surface oxide removal gas source, the surface passivation layer deposition gas source, the inert gas purging gas source, the vacuum pump system, and the exhaust gas treatment module. The reaction chamber has a temperature-controllable heating module, a remote plasma module, and a gas spraying module.

[0056] The system comprises a heating module for heating III-V group devices, a remote plasma module for generating plasma to achieve film deposition, a gas spraying module for uniformly introducing gas into the reaction chamber, a surface oxide removal gas source for introducing reactive gas into the reaction chamber, a surface passivation layer deposition gas source for introducing gas for depositing oxide composite films and oxygen-free films into the reaction chamber, an inert gas purging gas source for purging the reaction chamber, and a vacuum pump system for evacuating the reaction chamber. The surface passivation layer deposition gas source is equipped with a high-speed switching control valve, enabling basic atomic layer thin film deposition functions.

[0057] In some examples, the heating module includes a substrate heating source and a sidewall heating source, the substrate heating source being used to heat the stage carrying the III-V device, and the sidewall heating source being used to heat the inner sidewall of the reaction chamber.

[0058] The process of implementing the passivation method for the III-V group devices using the passivation equipment provided by this invention is as follows:

[0059] The first step is to heat the reaction chamber to the specified temperature, place the cleaved semiconductor laser in the reaction chamber, and use a high-purity inert gas purging gas source and vacuum pump system to cycle through vacuuming and inert gas purging multiple times to remove oxygen and water vapor in the chamber as much as possible.

[0060] The second step involves removing the surface oxide layer by introducing one or more reactive gases to achieve self-limiting removal of the natural oxide layer. The introduction of reactive gases can follow the procedure below: ① Introduce one reactive gas; ② Stop the introduction and operate the vacuum pump system; ③ Purge the source with high-purity inert gas and operate the vacuum pump system; ④ Introduce one reactive gas; ⑤ Stop the introduction and operate the vacuum pump system; ⑥ Purge the source with high-purity inert gas and operate the vacuum pump system. The process of introducing reactive gases and purging can be repeated to ensure that the natural oxide layer is completely removed.

[0061] The third step involves repeatedly operating the vacuum pump system and purging the high-purity inert gas source over a long period of time to remove as many gaseous products as possible.

[0062] The fourth step involves the surface suspension passivation gas source working, and at the same time, the remote plasma module can be optionally activated to introduce atomic H, low-energy N plasma or S-containing compounds, so that the surface suspension bonds or surface states are hydrogenated, nitrided or sulfided, reducing the surface state density.

[0063] The fifth step involves repeatedly operating the vacuum pump system and purging the high-purity inert gas source over a long period of time to remove as much residual gaseous compound as possible.

[0064] Step 6: Deposit surface passivation layer using gas source to deposit the surface passivation layer;

[0065] The seventh step involves repeatedly operating the vacuum pump system and purging the high-purity inert gas source over a long period of time to remove as much residual gaseous compounds as possible.

[0066] Throughout the above steps, the exhaust gas treatment module remains operational, treating the working gas source for each step in a pollution-free manner.

[0067] This invention addresses the shortcomings of existing sidewall passivation technologies for semiconductor III-V group materials, such as incomplete removal of oxide layers (including aluminum oxide, gallium oxide, indium oxide, arsenic oxide, etc.), easy damage to the material surface, poor passivation layer density, and reliance on ultra-high vacuum cleavage (<10). -7～-8 The passivation method provided addresses the problems of high cost and low production efficiency caused by Torr and molecular beam epitaxy. It can achieve precise removal of various oxide layers and in-situ deposition of high-quality passivation layers, while reducing costs and improving production efficiency.

[0068] The passivation equipment provided by this invention can complete all steps within the same chamber by switching the surface oxide removal gas source, the surface suspension passivation gas source, and the surface passivation film deposition gas source, without the need for chamber switching. This avoids secondary oxidation caused by switching process chambers and equipment. The photoelectric properties of the passivated surface can achieve the same photoelectric properties as samples processed by ultra-high vacuum dissociation and molecular beam epitaxy coating equipment. Moreover, this invention does not rely on ultra-high vacuum, resulting in lower costs and the same effect. This allows semiconductor wafers based on III-V materials to be cleaved or scratched in air, which is beneficial for significantly increasing production capacity, greatly improving production efficiency, and effectively reducing costs.

[0069] It should be understood that the various forms of processes shown above can be used to reorder, add, or delete steps. For example, the steps described in this invention disclosure can be executed in parallel, sequentially, or in different orders, as long as the desired result of the technical solution disclosed in this invention can be achieved, and this is not limited herein.

[0070] The specific embodiments described above do not constitute a limitation on the scope of protection of this invention. Those skilled in the art should understand that various modifications, combinations, sub-combinations, and substitutions can be made according to design requirements and other factors. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A passivation method for a III-V group device, characterized in that, include: A III-V device is provided, the III-V device having a III-V material surface, the III-V material surface having a native oxide layer; The III-V device is placed in a reaction chamber, and a reaction gas is introduced into the reaction chamber. The reaction gas reacts with the native oxide layer to generate volatile products, thereby removing the native oxide layer in a self-limiting manner. The reaction chamber is purged to remove volatile products and excess reaction gases; An oxygen-free thin film is deposited in situ on the surface of the III-V group material using the reaction chamber, and then an oxide composite film is formed on the surface of the oxygen-free thin film.

2. The passivation method for III-V group devices according to claim 1, characterized in that, The natural oxide layer includes at least one of aluminum oxide, gallium oxide, indium oxide, and arsenic oxide.

3. The passivation method for III-V group devices according to claim 1, characterized in that, The process temperature for introducing reactive gas into the reaction chamber to remove the natural oxide layer is in the range of 20°C to 500°C. The process of introducing reaction gas into the reaction chamber to remove the natural oxide layer includes: performing one round of reaction or performing multiple rounds of the same reaction. For multiple rounds of the same reaction, a purging process is performed between two rounds of reaction to remove volatile products and excess reaction gas generated in the previous round of reaction.

4. The passivation method for III-V group devices according to claim 3, characterized in that, Each round of reaction introduces either one type of reaction gas or N different types of reaction gases; For each round of reaction, N different reaction gases are introduced in sequence. If n is defined as the sequence number of the reaction gases, the (n+1)th reaction gas is used to react with the non-volatile byproducts generated in the previous reaction to generate volatile products, or the (n+1)th reaction gas is used to remove the remaining natural oxide layer that was not removed in the previous reaction.

5. The passivation method for III-V group devices according to claim 3, characterized in that, For the introduction of a reaction gas, the reaction gas includes one of the following: Cl2, CCl4, CHCl3, CH2Cl2, BCl3, HCl, NH4Cl, C5H9Cl, SiCl4, TiCl4, SbCl5, PCl3, InI3, Na2S2O3, H2S, (NH2)2CS, thiols, sulfonyl compounds, sulfonic acid compounds, sulfonate esters, sulfonamides, thiocarboxylic acids and their derivatives, DMF, low-energy Ar plasma, low-energy N plasma, and low-energy H plasma; For the introduction of N different reaction gases, the first reaction gas introduced includes one of the following: CCl4, CHCl3, CH2Cl2, HCl, SiCl4, TiCl4, BCl3, HF, Hhfac, NF3, CF4, a mixture of CF4 and H2, SF6, NH4F, BF3, PF5, XeF2, CHF3, and NH4HF2. The remaining reaction gases introduced each time after the first introduction include one of the following: low-energy Ar plasma, low-energy H plasma, DMAC, TMA, Sn(acac)2, H2S, InI3, carbonyl sulfide, (NH2)2CS, Ga(NMe2)3, trimethyl borate, Al(NMe2)3, TMGa, TEGa, TMI, DMZn, thiols, thioethers, sulfonyl compounds, sulfonamides, thiocarboxylic acids and their derivatives, BTBAS, and ZDEC. Low energy refers to energy less than a preset value, which is in the range of 20eV to 30eV.

6. The passivation method for III-V group devices according to claim 1, characterized in that, Before forming an oxygen-free film after removing the natural oxide layer, the process further includes: using atomic H, low-energy N plasma, or S-containing compounds to remove surface dangling bonds or surface states on the surface of the III-V group material to reduce the surface state density.

7. The passivation method for III-V group devices according to claim 1, characterized in that, The formation of the oxygen-free film includes: in-situ deposition of an oxygen-free film on the surface of the III-V group material using a non-plasma-enhanced deposition process; The formation of the oxide composite film includes: forming an oxide composite film on the surface of the oxygen-free film using a plasma-enhanced atomic layer deposition process.

8. The passivation method for III-V group devices according to claim 7, characterized in that, The non-plasma-enhanced deposition process includes thermal atomic layer deposition.

9. The passivation method for III-V group devices according to claim 1, characterized in that, Li2S, LiN3, LiF, LiAl x F y 、LiAl x S y 、Lift-CF x 、BN、CoC x 、ErC2、FeC x 、MoC x 、NbC x 、NiC x 、SiC、TaC x 、TiC x 、Toilet x 、HfAl x C y 、MoC x N y 、SiC x N y 、TaC x N y 、TiC x N y 、Toilet x N y 、TaAl x N y Cz、NaF、MgF2、MgTe、Al2S3、AlAs、AlF3、AlN、AlP、AlSb、Al:MoS2、AlGa x As y 、AlGa x N y 、AlW x F y 、CuAl x S y 、HfAl x C y 、InAl x N y 、RuAl x N y 、Sc x Heavy y F z 、TiAl x C y 、TiAl x N y 、AlIn x Ga y N z 、Si、CoSi2、NbSi、Si3N4、SiC、TaSi x 、Russian x N y 、SiC x N y 、WSi x N y 、AlP、CoP x GaP, InP, MoP, GaAs x P y 、GaIn x P y CuCl, PbCl2, PbBr x Cl y 、PbI x Cl y CaF2, CaS, CaSnS, SnCa x S y 、ScF3、ScN、Sc x To the y F z TiN TiC x TiS2, TiS3, CoTi x N y 、NbTi x N y 、RuTi x N y ,Tic x N y ,Thyme x N y 、TiV x N y 、VN、VS x 、TiV x N y 、VIn x S3y、MnAs、MnF2、MnS、MnTe、ZnMn x S y 、FeC x 、FeN x 、FeS x 、FeSe x 、Co3Sn2、Co x S y 、CoC x CoF2 CoN x 、CoP x 、CoS2、CoSe2、CoSi2、CoTi x N y 、FeCo x S y 、Ni2Ge、Ni3N、Ni3Sn2、NiC x NiF2 NiS x NiSe2 PtNi x Cu3N, CuCl, CuMn x CuSe x CuS x Cu:ZnS x CuAl x S y CuGa x S y CuIn x S y CuSb x S y CuSn x S y CuZn x S y CuZn x Sn y S z FeZn x 、Zn3N2、ZnF2、ZnS、ZnSe、ZnTe、ZnIn x S y ZnMn x S y ZnSn x S y ZnS x Se y CdZn x Ga y S z 、GaAs、GaN、GaP、GaSb、GaS x CuGa x S y GaAs x P y GaIn x P y InGa x As y InGa x N y AlIn x Ga y N z CdZn x Ga y S z GeS, GeSb, GeSe, GeS x Gete x Ni2Ge, GeSb x Te y GeS x Se y Gete x S y GeSb x Se y Te z As2S3, InAs, MnAs, PbBr2, PbBr x Cl y 、PbBr x I y SrF2, SrS, SrCe x S y 、SrS x Se y 、SrTb x S y YF3, ZrF4, ZrN x 、ZrS2、NbC x 、NbN、NbSi、NbTi x N y 、MoC x 、MoN x MoP, MoS2, MoSe2, MoTe2, Al:MoS2, MoC x N y 、TiMo x N y 、RuPt x ,Route x N y 、RuTi x N y CdS, CdSe, CdTe, CdSe x Te y 、CdZn x S y 、CdZn x Ga y S z In2S3, In2Se3, InN, InSb, InSe, SnI2, SnN x 、SnSe x 、SnS x SnTe, CaSnS, CsSnI3, Sb2S3, Sb2Se3, Sb2Te3, SbSe x Te y CsI, PbI2, CsPbI3, BaS, HfF4, HfN x HfS2 and HfAl x C y Thanks for reading. The oxide composite film comprises stacked Al2O3 layers and SiO2 layers; The thickness of the oxidized composite film is greater than the thickness of the oxygen-free film.

10. A passivation apparatus for a III-V group device, characterized in that, A passivation method for implementing any one of claims 1 to 9 for a III-V group device, the passivation equipment for the III-V group device comprising: a reaction chamber, a surface oxide removal gas source, a surface passivation layer deposition gas source, an inert gas purging gas source, a vacuum pump system, a control system, and an exhaust gas treatment module, wherein the surface oxide removal gas source, the surface passivation layer deposition gas source, the inert gas purging gas source, the vacuum pump system, and the exhaust gas treatment module are all connected to the reaction chamber, and the control system is used to control the surface oxide removal gas source, the surface passivation layer deposition gas source, the inert gas purging gas source, the vacuum pump system, and the exhaust gas treatment module, and the reaction chamber having a temperature-controllable heating module, a remote plasma module, and a gas spraying module.

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