CN115986555A - Resonant cavity surface passivation film of semiconductor laser device, manufacturing method and device - Google Patents
Resonant cavity surface passivation film of semiconductor laser device, manufacturing method and device Download PDFInfo
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Abstract
The application discloses passive film of resonant cavity surface of semiconductor laser device, manufacturing method and device, the passive film of resonant cavity surface includes: a passivation layer and a protective layer. The passivation layer directly covers the resonant cavity surface of the semiconductor laser device; and the protective layer covers the passivation layer, the passivation layer and the protective layer are manufactured and formed in the same sulfur-containing compound solution, and the protective layer is made of a wide-band-gap sulfur oxide material. By means of the mode, the semiconductor laser device can be improved in the capability of resisting damage of the optical mirror surface of the semiconductor laser device, the highest output power of the semiconductor laser device is improved, the passive film of the resonant cavity surface is effective for a long time, the reliability of the semiconductor laser device is further enhanced, and the service life of the semiconductor laser device is prolonged.
Description
Technical Field
The application relates to the technical field of semiconductor surface region selective passivation, in particular to a resonant cavity surface passivation film of a semiconductor laser device, a manufacturing method and a device.
Background
COMD (Catastrophic optical mirror Damage) is an important factor affecting the reliability, lifetime, and maximum output power of a high-power semiconductor laser. When laser is output, strong light radiation flux in the resonant cavity passes through the resonant cavity surface, electrons and holes are subjected to non-radiative recombination on the resonant cavity surface, the temperature is increased, the band gap width of the material is reduced due to the increase of the temperature, the absorption of the resonant cavity surface to the laser is accelerated, the oxidation of the resonant cavity surface and the diffusion of defects are accelerated, the surface state density of the resonant cavity surface is increased due to the oxidation, the non-radiative recombination in the area of the resonant cavity surface is accelerated, a positive feedback process is formed, and when the temperature of the resonant cavity surface exceeds the melting point of the material, the resonant cavity surface is melted, so that a semiconductor laser device is disabled.
The resonant cavity surface passivation technology of the semiconductor laser is one of effective methods for slowing down the COMD, can improve the COMD resistance and reliability of the semiconductor laser, and prolongs the service life of the semiconductor laser. In the prior art, the most successful passivation technology for relieving the catastrophe problem of the resonant cavity surface is to dissociate the wafer in ultrahigh vacuum to generate bars and plate silicon on the resonant cavity surface, but the method is not easy to operate, has high cost and low production efficiency, so that the mass production technology for dissociating the wafer in atmospheric environment to generate bars and then passivating the resonant cavity surface is particularly focused on the research and development. The sulfuration method is an effective method for removing natural oxides (native oxides) and surface defects on the surface of a compound semiconductor, and can effectively improve the threshold value of COMD generated by a semiconductor laser device.
Wet vulcanization is widely used because of its simplicity and low cost, but it has the following problems: the passivation film formed on the cavity surface of the resonator by wet vulcanization is easily oxidized again or volatilized, so that the passivation effect of the passivation film is ineffective, therefore, the passivation film needs to be protected immediately after being formed, and the stability of the passivation film is maintained.
Disclosure of Invention
The technical problem mainly solved by the application is to provide a method for manufacturing a resonant cavity surface passivation film of a semiconductor laser device, which can improve the threshold value of generating COMD and enable the resonant cavity surface passivation film to be effective for a long time, thereby improving the reliability of the semiconductor laser device and prolonging the service life of the semiconductor laser device. Meanwhile, the method is a novel regional selective passivation technology, and a passivation film is almost only formed on the resonant cavity surface of the semiconductor laser device.
In order to solve the technical problem, the application adopts a technical scheme that: provided is a resonator surface passivation film of a semiconductor laser device, the resonator surface passivation film including: the passivation layer covers the resonant cavity surface of the semiconductor laser device; and the protective layer covers the passivation layer, the passivation layer and the protective layer are manufactured and formed in the same sulfur-containing compound solution, and the protective layer is made of a wide-band-gap sulfur oxide material.
In order to solve the technical problem, the other technical scheme adopted by the application is as follows: the semiconductor laser device comprises a resonant cavity surface passivation film, wherein the resonant cavity surface passivation film is the resonant cavity surface passivation film provided by the technical scheme.
In order to solve the technical problem, the application adopts a technical scheme that: a method for manufacturing a passive film of a resonant cavity surface of a semiconductor laser device is provided, which comprises the following steps: covering a thin film of a vulcanization passivation layer on the resonant cavity surface of the semiconductor laser device; and covering a protective layer film on the passivation layer by adopting a photochemical deposition method, wherein the protective layer is made of a wide-band-gap oxysulfide material. The passivation layer and the protective layer are formed in the same sulfur-containing compound solution.
The beneficial effect of this application is: unlike the case of the prior art, the resonator surface passivation film of the present application includes: a passivation layer covering the resonant cavity surface of the semiconductor laser device; and the protective layer covers the passivation layer, the passivation layer and the protective layer are manufactured and formed in the same sulfur-containing compound solution, and the protective layer is made of a wide-band-gap sulfur oxide material. The role of the passivation layer process includes two aspects: (1) Natural oxides, pollution and surface defects on the surface of the resonant cavity surface, which are generated due to the contact of the resonant cavity surface and air, are removed, and the suspended bonds on the resonant cavity surface are saturated by the passivation layer material, so that the surface state density is reduced; (2) A compact passivation layer is formed on the surface of the resonant cavity, so that the semiconductor is isolated from the outside and reoxidation is avoided. Furthermore, the passivation layer and the protective layer are formed in the same sulfur-containing compound solution, so that the manufacturing process can be simplified, and the manufacturing efficiency of the passive film of the resonant cavity surface can be improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings used in the description of the embodiments will be briefly described below. Wherein:
FIG. 1 is a schematic structural diagram of an embodiment of a resonant cavity surface passivation film of a semiconductor laser device according to the present application;
FIG. 2 is a schematic structural diagram of an embodiment of a semiconductor laser device according to the present application;
FIG. 3 is a flow chart of one embodiment of a method for fabricating a passive film on a cavity surface of a semiconductor laser device according to the present invention;
FIG. 4 is a schematic view of a laser diode resonator cavity surface finished passivation film of a semiconductor laser device of the present application;
fig. 5 is a schematic diagram of an apparatus for manufacturing a passivation film for a resonator surface and a protective layer of a wide bandgap sulfur oxide made of PCD according to an embodiment of the present invention.
FIG. 6 shows passivation of the sulfide and Zn (S) in accordance with the present application 1-δ O δ ) The protective layer is applied to the output power-current relation graph of a semiconductor laser device with the wavelength of 1064nm, the solid line shows that the semiconductor laser device is provided with an implemented passivation film, the dotted line shows that the semiconductor laser device is provided with vulcanization passivation but does not contain Zn (S) 1-δ O δ ) And a protective layer, wherein the power of COMD generation of the former is about 50% higher than that of the latter.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments.
Prior to setting forth the detailed description of the present application, the state of the art to which the present application pertains will be described.
The passivation technology of the resonant cavity surface of the semiconductor laser is one of effective methods for improving the threshold value of the generated COMD and simultaneously slowing down the COMD, can improve the COMD resistance and reliability of the semiconductor laser and prolong the service life of the semiconductor laser. In the prior art, the most successful passivation technology for relieving the catastrophe problem of the resonant cavity surface is a technology for dissociating a wafer in ultrahigh vacuum to generate bars and plating silicon on the resonant cavity surface, but the passivation method is not easy to operate, has high cost and low production efficiency, and then the bars are dissociated in the atmospheric environment and the resonant cavity surface is passivated. The main principle of the resonant cavity surface passivation technology after the bars are dissociated in the atmospheric environment comprises two aspects: firstly, removing natural oxides, pollution and surface defects on the surface of the resonant cavity surface, which are generated by the contact of the resonant cavity surface and air, manufacturing a passivation layer saturated resonant cavity surface dangling bond, isolating a semiconductor from being in contact with the outside, and preventing the semiconductor from being reoxidized, wherein a wet method or a dry method is usually adopted; secondly, a dense dielectric film is formed on the surface of the resonant cavity to protect the passivation layer, so that the passivation layer is effective for a long time, and physical vapor deposition or chemical vapor deposition is usually adopted.
The sulfurization method is an effective method for removing natural oxides, pollution and surface defects on the surface of a compound semiconductor, and can improve the threshold value of COMD generation of a semiconductor laser device. The sulfuration method is divided into wet sulfuration and dry sulfuration, and wet sulfuration is reported mostly, mainly by using sulfur-containing solution to react with semiconductor, while dry sulfuration is generally used for processing semiconductor by using sulfur-containing plasma. Wet-sulfiding of the cavity surface of a semiconductor laser refers to immersing the cavity surface in a solution containing sulfur, such as ammonium sulfide ((NH) 4 ) 2 S), sodium sulfide (Na) 2 S), thiourea (CS (NH) 2 ) 2 ) Or thioacetamide (CH) 3 CSNH 2 ) The water solution or/and the organic solution to remove natural oxides, pollution and surface defects of the resonant cavity surface, and then forming a sulfide and sulfur passivation layer, namely a film after the vulcanization reaction, on the resonant cavity surface. Although the wet vulcanization is simple to operate and low in cost, the following problems exist: the sulfide and sulfur with a plurality of atomic layers to tens of atomic layers on the surface of the resonant cavity surface play a passivation role in the vulcanization method, and after the vulcanized resonant cavity surface is placed in the air for a period of time, the sulfur can be oxidized or volatilized, so that the semiconductor material on the resonant cavity surface is oxidized again, and the passivation effect is ineffective. In addition, even if the laser chip vulcanized on the resonant cavity surface is taken out of the solution, dried and then quickly placed in the coating equipment for subsequent deposition of the optical film on the resonant cavity surface, the vulcanization failure of the resonant cavity surface still can be caused at a high probability becauseThe deposition of optical films is typically performed in a vacuum and/or heated high temperature environment, which is more prone to sulfur volatilization, resulting in the deactivation of the passivation effect of wet-vulcanization.
According to the semiconductor laser device, after the surface of the resonant cavity of the semiconductor laser device is covered with the vulcanized passivation layer, the passivation layer is immediately covered with the protective layer, and the protective layer is made of a wide-band-gap sulfur oxide material, so that the disappearance of sulfur on the surface of the resonant cavity can be prevented. The effect of the resonant cavity surface passivation film of the semiconductor laser device of the present application mainly includes two aspects, namely, the passivation effect and the stability thereof. The wide-band-gap oxysulfide material is selected as the protective layer material, so that the protective layer material can be prevented from absorbing laser, and the passivation layer material is prevented from being invalid.
The present application will be described in detail with reference to the drawings and embodiments.
Referring to fig. 1, fig. 1 is a schematic structural diagram of an embodiment of a resonant cavity surface passivation film of a semiconductor laser device of the present application, where the resonant cavity surface passivation film 100 includes: a passivation layer 101 and a protective layer 102.
The passivation layer 101 covers the resonant cavity surface of the semiconductor laser device; the passivation layer 101 is covered with the protection layer 102, the passivation layer 101 and the protection layer 102 are formed in the same sulfur-containing compound solution, and the protection layer 102 is made of a wide band gap material.
In practical applications, the film of the wide band gap material of the protection layer 102 may be a part of or all of a subsequent resonator surface optical film of the semiconductor laser device, and after the resonator surface passivation film 100 is completed, another material film may be plated to adjust the reflectivity, so as to achieve the designed characteristics of the semiconductor laser device, for example: coating Al on one end of resonant cavity surface of semiconductor laser device 2 O 3 、SiO 2 And TiO 2 The film was such that the overall reflectance including the passivation film 100 was 5%, and the other end was plated with Al 2 O 3 、SiO 2 And TiO 2 The multilayer film structure makes the overall reflectivity of the passivation film 100 be 99%, and the passivation layer 101 is not degraded by the subsequent optical film plating process due to the protective layer 102.
In the embodiment of the present application, after the resonant cavity surface of the semiconductor laser device is covered with the passivation layer 101, the passivation layer 101 is immediately covered with the protective layer 102, and the protective layer 102 is made of a wide band gap material, so that the passivation layer 101 on the resonant cavity surface can be prevented from failing. The role of the resonator surface passivation film 100 of the semiconductor laser device of the present application mainly includes two aspects, namely, the passivation effect and the stability thereof. By selecting the material for immediately depositing the wide band gap material as the protective layer 102, the material of the passivation layer 101 can be prevented from being oxidized or volatilized, the material failure of the passivation layer 101 is prevented, and the absorption of the material of the protective layer 102 on laser photons is prevented. Further, the passivation layer 101 and the protection layer 102 are formed in the same sulfur-containing compound solution, so that the manufacturing process can be simplified, and the manufacturing efficiency of the passive film on the cavity surface of the resonator can be improved.
In one embodiment, the passivation layer 101 is a sulfur-containing thin film formed by reacting a semiconductor epitaxial material of a resonant cavity surface of a semiconductor laser device with a sulfur-containing compound in a sulfur-containing compound solution.
The sulfide thin film formed by the reaction of the resonant cavity surface of the semiconductor laser device and the sulfur-containing compound may be formed by a dry process or a wet process. Wet sulfidation, which is mainly a reaction between a sulfur-containing compound solution and a semiconductor, is reported, whereas dry sulfidation is a treatment of a semiconductor using a sulfur-containing plasma. In general, wet sulfidation of the cavity surface of the semiconductor laser device means that the cavity surface is immersed in a solution of a compound containing sulfur, for example, an aqueous solution or/and an organic solution of ammonium sulfide, sodium sulfide, thiourea or thioacetamide, to remove natural oxides and contamination of the cavity surface, and then a sulfide passivation layer, i.e., a sulfur-containing thin film after sulfidation reaction, is formed on the cavity surface. In the present application, thiosulfate can be used instead of the sulfide, and specifically, the solution of the sulfur-containing compound at least contains a sulfide solution of thiosulfate, and the solvent is water or an organic solution, or a mixed solution of water and an organic solution. Another advantage of using thiosulfate is that it is odorless and environmentally friendly, unlike the aforementioned ammonium sulfide, sodium sulfide, thiourea or thioacetamide which can emit odors.
In one embodiment, the chemical solution in the sulfidation passivation process contains thiosulfate ions (S) 2 O 3 2- ) Thiosulfonate (R-S) 2 O 2 - ) Thiophosphate (SPO) 3- ) Or dithiophosphoric acid radical (S) 2 PO 2 3- ) As a source of sulfur for the passivation layer 101.
The passivation layer 101 has a thickness of several atomic layers to several tens of atomic layers.
In one embodiment, the material of the protective layer 102 is a wide band gap sulfur oxide material; the thickness of the protective layer 102 is 1-800nm, for example: 1nm, 5nm, 10nm, 100nm, 200nm, 400nm, 600nm, 800nm, or the like.
In this embodiment, the material of the protection layer 102 is selected to be a wide band gap oxysulfide material, which can prevent the material of the protection layer 102 from absorbing laser photons and prevent the material of the passivation layer 101 from being oxidized or volatilized, and the materials of the passivation layer 101 and the protection layer 102 are both sulfur-containing compounds and are matched with each other; on the other hand, the material of the protective layer 102 is a wide-bandgap sulfur oxide material, and the formation process of the material can be matched with the process of the sulfide passivation layer, that is, both processes are performed in the same sulfur-containing compound solution.
In one embodiment, the wet process for depositing the oxysulfide film includes PCD (Photochemical Deposition), chemical Bath Deposition (CBD), electroplating, and the like.
Compared with other methods, the PCD method has the advantages of deposition area selectivity (namely, the oxysulfide film is deposited only in the area irradiated by ultraviolet light), simple and convenient process, low cost, no need of expensive vacuum devices, easy control of experimental conditions and easy matching and integration with the wet vulcanization process of the passivation layer.
Wherein, in the deposition process of the wide-band-gap oxysulfide film (protective layer), ultraviolet light is adopted to irradiate the resonant cavity surface of the semiconductor laser device. Further, the irradiation manner using ultraviolet light is continuous irradiation or intermittent irradiation. Further, the wavelength of the ultraviolet light is less than 400nm. The light source of ultraviolet light comprises Ar 2 *、Kr 2 *、Xe 2 *、F 2 *、Cl 2 *、Br 2 *、I 2 * NeF, arF, arCl, arBr, krF, krCl, krBr, krI, xeF, xeCl, xeBr, xeI, excimer lamp, mercury lamp, xenon mercury lamp, deuterium arc lamp, hydrogen arc lamp, xenon-antimony arc lamp, carbon arc lamp, metal halide lamp, UV-B ultraviolet lamp, ultraviolet light emitting diode, and ultraviolet laser.
In one embodiment, the chemical solution in the PCD method contains thiosulfate ions (S) 2 O 3 2- ) Thiosulfonate (R-S) 2 O 2 - ) Thiophosphate (SPO) 3- ) Or dithiophosphoric acid radical (S) 2 PO 2 3- ) As a source of sulfur for the wide band gap sulfur oxides.
In one embodiment, the chemical solution of the PCD method comprises at least one ion or complex ion of zinc, cadmium, magnesium, calcium, strontium, barium, aluminum, gallium, indium, tin, antimony, bismuth, or manganese as a source of a cation of the wide band gap sulfur oxide.
Taking zinc oxysulfide as an example, the ph value, deposition temperature, ultraviolet irradiation mode and time, zn to S equivalent ratio, metal ion complexing agent, distance from ultraviolet irradiation penetrating through the solution to the resonant cavity surface, etc. of the solution in the PCD system may affect the deposition rate, oxygen content, stress state, transmittance, compactness, surface morphology, etc. of the wide-bandgap zinc oxysulfide film. As long as a proper solution formula and parameters are adopted, the PCD wide-band gap oxysulfide film can achieve the characteristics of high deposition rate, low oxygen content, small stress, high transmissivity, high compactness and uniform coverage of the film. The PCD can accurately control the deposition position of the wide-band-gap oxysulfide film through selective irradiation of ultraviolet light, and the ultraviolet light is adopted to selectively irradiate the resonant cavity surface of the semiconductor laser device, so that the oxysulfide film is only deposited on the resonant cavity surface, which just meets the requirement of a passive film of the resonant cavity surface, avoids deposition in a non-resonant cavity surface area, and facilitates the integration of the manufacturing process of the semiconductor laser device.
Listing the chemical reaction of PCD zinc sulfide (ZnS) thin films to illustrate the regioselective deposition, zinc sulfide results in the chemical reaction formula:
Zn 2+ +S+2e - →ZnS[1]
where zinc ions, sulfur atoms and electrons are required;
the photochemical reaction of thiosulfate can provide a sulfur atom and an electron, which are:
S 2 O 3 2- +hν→S+SO 3 2- [2]
2S 2 O 3 2- +hν→S 4 O 6 2- +2e - [3]
S 2 O 3 2- +SO 3 2- +hν→S 3 O 6 2- +2e - [4]
wherein, hv represents ultraviolet light photons.
The zinc ions can be supplied by adding a zinc-containing salt, and thus, a zinc sulfide thin film can be produced by irradiating the solution containing the necessary components that react to form zinc sulfide with ultraviolet light.
In addition, thiosulfuric acid is a di-protic acid that dissociates in aqueous solution to produce HS 2 O 3 - And S 2 O 3 2- ：
At constant temperature H 2 S 2 O 3 、HS 2 O 3 - And S 2 O 3 2- The concentration will reach the equilibrium, H in the solution 2 S 2 O 3 、HS 2 O 3 - And S 2 O 3 2- And coexisting.
In an acidic solution, the reaction of thiosulfate ions and hydrogen ions produces sulfur atoms as follows:
this reaction, although providing sulfur atoms, does not generate electrons in the absence of uv irradiation, and therefore cannot form a ZnS thin film, and only the uv-irradiated region has the deposition of a ZnS thin film, which is a trigger for the regioselectivity of PCD and also for providing passivation by sulfurization.
The zinc ions in the solution of PCD originate from zinc-containing salts, such as: zinc sulfate (ZnSO) 4 ) Etc., the sulfur atom is mainly derived from thiosulfate (S) 2 O 3 2- ) Photochemical reaction under ultraviolet irradiation, and pH regulator of the solution is usually sulfuric acid (H) 2 SO 4 ) Or ammonia, etc., the complexing agent is usually ethylenediamine tetraacetic acid (EDTA, C) 10 H 16 N 2 O 8 ) Tartaric acid (C) 4 H 6 O 6 ) Citric acid (CO), etc., the complexing agent functions to reduce Zn in solution 2+ Ion concentration to prevent Zn from being excessive or forming Zn (OH) when ZnS is formed 2 And (4) precipitating.
While the PCD reaction is in progress, other parallel chemical reactions also occur simultaneously, including metal ions and OH in solution - The ions react to form hydroxides, zincExample (c):
therefore, oxygen is inevitably contained in the plating film mainly because water molecules and the above-mentioned metal ions combined with hydrogen and oxygen are occluded in the plating film as sulfides are deposited, and generally expressed in the form of Zn (S, O, OH) or Zn (S, OH), in which the hydrogen content is not easily measured, and generally hydrogen has no significant influence on the use, so hydrogen is often ignored, and therefore, for such sulfide plating films, M is used in the present application m (S 1-δ O δ ) n M represents a metal atom, M and n represent a compound stoichiometric ratio, and δ is an oxygen content; other impurity elements such as carbon, nitrogen and the like exist, but the content ratio is very low, the film coating property is hardly influenced, and the attention is not paid to neglect.
The formation of the passivation layer is carried out before the PCD reaction for manufacturing the protective layer is carried out, the solution used at this stage is the same solution as the solution for manufacturing the protective layer by the PCD method, but the solution is not irradiated by ultraviolet light, so the PCD reaction does not occur, and oxysulfide is not generated, for example: zn (S) 1-δ O δ ) The thiosulfate in the solution reacts with the hydrogen ion to generate a sulfur atom, as shown in the above chemical reaction formula [7 ]]Shown by this sulfur atom and/orThe hydrogen ions react with the semiconductor material of the cavity surface of the laser, first dissolving the natural oxide on the surface, and then reacting to form a passivation layer of sulfide and sulfur, and possibly also a chemical replacement reaction of sulfur and oxygen, where the sulfur and sulfide thin film is the passivation layer 101 of fig. 1. This passivation layer 101 plus a subsequently plated protective layer 102 forms the passivation film 100 of fig. 1.
The sulfuration reaction for forming the passivation layer 101 should be carefully selected from sulfur-containing reactants, and some sulfides will generate S after dissolving in water 2- Or/and HS - Ions, for example: the sulfide-containing ions can immediately react with metal ions in a solution to generate sulfides to be plated on the surface of the resonant cavity, namely CBD (cubic boron nitride), and the sulfides also have a passivation effect but have a poor passivation effect probably because natural oxides on the surface of the resonant cavity are not sufficiently removed before the sulfides are plated. The present application is mainly illustrated by thiosulfate as an example, but substances having the same efficacy are not limited to thiosulfate, and others such as: thiophosphate (PSO) 3 3- ) Dithiophosphoric acid radical (PS) 2 O 2 3- ) Thiosulfonate (S2O) 4 3- ) Etc. also have similar passivation effects and are suitable for subsequent PCD reactions.
The process of forming the passivation layer by the sulfidation reaction only describes the sulfidation reaction of the sulfur-containing anions with the cavity surface, however, metal cations are still present in the solution, and the chemical reaction of the metal ions with the cavity surface must be considered, and other chemical reactions competing with sulfidation may exist. When the electrochemical potential of the metal ions in the solution is higher than that of the epitaxial or substrate material, the epitaxial or substrate material is oxidized and converted into ions, and the ions are dissolved in the solution, and meanwhile, the metal ions existing in the solution are reduced into metal atoms and attached to the cavity surface, which can be schematically illustrated by the following simplified chemical reaction formula:
M + +GaAs→M (GaAs) +Ga 3+ [13]
M + +GaAs+H 2 O→M (GaAs) +H 2 AsO 4 - [14]
M + represents a metal ion in solution, M (GaAs) Indicating the attachment of a metal to a GaAs surface.
Taking copper as an example, if the solution contains copper ions, the electrochemical potential of the solution is higher than that of epitaxial materials such as: inGaAs or InGaP or substrate materials such as: gaAs or InP is high, and therefore, copper ions are reduced to copper atoms and adhere to the surface of an epitaxial material or a substrate material to form a copper plating film, which destroys the passivation film structure. Therefore, the material of the protective layer must be carefully selected according to the epitaxial and substrate materials when designing the passivation film structure, so as to avoid the generation of a metal coating film during the passivation process and the inclusion of the metal coating film between the passivation film and the epitaxial semiconductor material. Based on the above consideration, zinc sulfide is one of good choices, the electrochemical potential of zinc ions is low, zinc ions are not reduced to metallic zinc during passivation process, and the band gap width (3.54 eV) is large and larger than the photon energy of most semiconductor laser devices, and the absorption to laser is very low, so the application mainly takes zinc sulfide as an example for illustration, and the selection of other sulfide with smaller band gap width needs to satisfy the principle that the band gap width of the protective layer material is larger than the photon energy of laser, so as to avoid the laser being absorbed in large amount, and reduce the resistance and reliability of the COMD.
In one embodiment, the wide bandgap sulfur oxide material specifically includes: zn (S) 1-δ O δ )、Cd(S 1-δ O δ )、Mg(S 1-δ O δ )、Ca(S 1-δ O δ )、Sr(S 1-δ O δ )、Ba(S 1-δ O δ )、Al 2 (S 1-δ O δ ) 3 、Ga 2 (S 1-δ O δ ) 3 、In 2 (S 1-δ O δ ) 3 、Sn(S 1-δ O δ ) 2 、Sn(S 1-δ O δ )、Sb 2 (S 1-δ O δ ) 3 、Bi 2 (S 1-δ O δ ) 3 、Mn(S 1-δ O δ ) That is, the wide bandgap sulfur oxide material may be the material aloneThe material may be a mixture of two or more materials, where δ represents the content of oxygen atoms in the sulfur oxide material, and δ is in the range of: 0.2 is more than or equal to delta and more than 0.
Further, the material of the protective layer 102 is a mixture containing a wide band gap sulfur oxide material; for example: the mixture containing the wide band gap sulfur oxide material includes: zn (S) 1-δ O δ ) And Cd (S) 1-ξ O ξ ) Mixture of (2), mg (S) 1-δ O δ ) And Ca (S) 1-ξ O ξ ) Sr (S) 1-δ O δ ) And Ba (S) 1-ξ O ξ ) Mixture of (2), al 2 (S 1-δ O δ ) 3 And Ga 2 (S 1-ξ O ξ ) 3 Mixture of (1), al 2 (S 1-δ O δ ) 3 And Mg (S) 1-ξ O ξ ) Mixture of (2), ca (S) 1-δ O δ ) And Sn (S) 1-ξ O ξ ) 2 The mixture containing the wide-gap sulfur oxide material may be one of the above-described mixtures, or may be a mixture of two or more of the above-described mixtures. Where δ represents the content of oxygen atoms in one oxysulfide material in the mixture, ξ represents the content of oxygen atoms in another oxysulfide material in the mixture, and the ranges of δ and ξ are: delta is more than 0.2 and more than or equal to 0 and xi is more than 0.2 and more than or equal to 0; for example: the mixture containing the wide-bandgap sulfur oxide material is Zn (S) 1-δ O δ ) And Cd (S) 1-ξ O ξ ) A mixture of (a); or Zn (S) 1-δ O δ )、Al 2 (S 1-δ O δ ) 3 And Mg (S) 1-δ O δ ) Mixtures of combinations of mixtures of (a) and (b), and the like.
Further, the material of the protective layer 102 is an alloy material of a wide band gap sulfur oxide; for example: the alloy material with the wide-gap sulfur oxide comprises (Zn) 1-x Cd x )(S 1-δ O δ )、(Mg 1-x Ca x )(S 1-δ O δ )、(Zn 1-x Ca x )(S 1-δ O δ )、(Ca 1-x Sr x )(S 1-δ O δ )、(Mg 1-x-y Ca x Ba y )(S 1-δ O δ )、(Al 1-x Ga x ) 2 (S 1-δ O δ ) 3 、(Zn 1-x Al x )(S 1-δ O δ )、(Zn 1-x Ga x )(S 1-δ O δ )、(Zn 1-x Mn x )(S 1-δ O δ )、(Zn 1-x-y Cd x Mn y )(S 1-δ O δ ) That is, the alloy material of the wide-gap sulfur oxide may be one of the above alloy materials, or may be a mixture of two or more of the above alloy materials. Wherein x is a content of one metal in an alloy material of one kind of wide band gap sulfur oxide (an alloy compound material of two metals), y is a content of the other metal in an alloy material of one kind of wide band gap sulfur oxide (an alloy compound material of three metals), δ represents a content of oxygen atoms in the sulfur oxide material, and ranges of x and y are: 1 > x, y > 0, δ ranging from: delta is more than 0.2 and more than 0.
The oxysulfides of these single or mixed or alloyed structures may be crystalline or Amorphous (Amorphous) or a mixture of these two structures.
With Zn (S) 1-δ O δ ) As an example of the wide band gap sulfur oxide, znS has a band gap width of 3.54eV, znO has a band gap width of 3.37eV, and a part of sulfur in ZnS is reduced in band gap width by replacing it with oxygen, and Zn (S) of PCD is decreased depending on the production conditions 1-δ O δ ) The optical band gap width of the film is in the range of 3.6-3.7eV, and the optical band gap width is wider than that of ZnS, mainly because the PCD film has small crystal particles and is based on the quantum confinement (quantum confinement) principle or quantum size effect (quantum size effect) and has larger optical band gap width than that of the bulk material. When sulfur oxides (e.g., zn (S)) are selected 1-δ O δ ) Has a band gap width larger than the photon energy of the laser (e.g., wavelength larger than 600 nm), has no intrinsic absorption and low absorption of the laser light emitted from the semiconductor laser, and has a small amount of oxygen in the ZnS film of PCD, which is not so small as to be able to absorb the laser lightThe passivation effect of the resonant cavity surface of the laser chip is influenced.
Referring to fig. 2, fig. 2 is a schematic structural diagram of an embodiment of the semiconductor laser device of the present application, and the semiconductor laser device 200 includes the cavity surface passivation film 100, and the cavity surface passivation film 100 is any one of the above-described cavity surface passivation films. For a detailed description of relevant contents, refer to the above detailed description of the resonant cavity surface passivation film 100, which is not described in detail herein.
Referring to fig. 3, fig. 3 is a flowchart of an embodiment of a method for manufacturing a cavity surface passivation film of a semiconductor laser device according to the present invention, which can manufacture the cavity surface passivation film of the semiconductor laser device, and please refer to the cavity surface passivation film of the semiconductor laser device for detailed description of related contents, which will not be described herein.
The method comprises the following steps: step S101 and step S102.
Step S101: and covering a thin film of a vulcanized passivation layer on the resonant cavity surface of the semiconductor laser device.
Step S102: and covering a protective layer film on the passivation layer, wherein the protective layer is made of a wide-band-gap oxysulfide material.
The passivation layer and the protective layer are formed in the same sulfur-containing compound solution.
In the embodiment of the application, after the passivation layer is covered on the resonant cavity surface of the semiconductor laser device, the passivation layer is immediately covered with the protective layer, and the protective layer is made of a wide-bandgap oxysulfide material, so that the passivation effect failure caused by the oxidation or volatilization of the passivation layer on the resonant cavity surface can be prevented. The role of the resonant cavity surface passivation film of the conductor laser device of the present application mainly includes two aspects, namely, the passivation effect and its stability. By selecting the broad-band-gap oxysulfide material as the protective layer material, the absorption of the protective layer material to laser photons can be reduced, the passivation layer material is prevented from being oxidized or volatilized, and the passivation layer material is prevented from being invalid.
Wherein, step S101 may specifically include: reacting a resonant cavity surface of the semiconductor laser device with a sulfur-containing compound solution to form a thin film containing sulfur and sulfide and covering the resonant cavity surface, wherein the thickness of the passivation layer is several atomic layers to tens of atomic layers. Forming a passivation layer on the resonant cavity surface of the semiconductor laser device by adopting a wet-process vulcanization method; the wet sulfiding process employs a sulfur-containing compound solution containing: a thiosulfate group; the solvent of the sulfur-containing compound solution is water or an organic solvent, or a mixed solution of water and an organic solvent.
Wherein, step S102 may specifically include: and covering a protective layer film on the passivation layer by adopting a PCD method. Wherein the sulfur-containing compound solution used contains thiosulfate ions as a source of sulfur for the wide-gap sulfur oxides; the sulfur-containing compound solution further comprises: at least one of zinc, cadmium, magnesium, calcium, strontium, barium, aluminum, gallium, indium, tin, antimony, bismuth or manganese ions or complex ions as a source of cations.
Wherein the wavelength of the ultraviolet light is less than 400nm; the light source of ultraviolet light includes: ar (Ar) 2 *、Kr 2 *、Xe 2 *、F 2 *、Cl 2 *、Br 2 *、I 2 * NeF, arF, arCl, arBr, krF, krCl, krBr, krI, xeF, xeBr, xeI, excimer lamp, mercury lamp, xenon-mercury lamp, deuterium arc lamp, hydrogen arc lamp, xenon-antimony arc lamp, carbon arc lamp, metal halide lamp, UV-B ultraviolet lamp, UV-led, UV laser.
Wherein, the material of the protective layer is a wide-band-gap oxysulfide material; the thickness of the protective layer is 1-800nm.
Referring to fig. 4, fig. 4 is a schematic diagram of a laser diode fabricated by performing wet-process passivation on the resonant cavity surface of a laser chip and then immediately forming a wide-bandgap oxysulfide film from PCD. In the figure, the cavity surface is covered with a film 1 containing sulfide and sulfur after a sulfurization reaction and a film 2 containing sulfur oxide with a wide band gap, respectively, in sequence, wherein the epitaxial structure comprises: active layer 3, waveguide layer 4, n-type cladding layer 5, p-type cladding layer 6, n-typeThe semiconductor device comprises a semiconductor substrate 7, an n-surface metal electrode 8, a p-surface metal electrode 9 and a p-type heavily doped semiconductor layer 10. The active layer 3, the waveguide layer 4, the cladding layers 5 and 6, and the semiconductor substrate 7 are made of different materials, for example: inGaP/[ (Al) with wavelength of 630-680nm x Ga 1-x ) 1-y In y ]P/[(Al u Ga 1-u ) 1-v In v ]In the P/GaAs epitaxial system, the active layer 3 is made of InGaP quantum well, and the waveguide layer 4 is made of [ (Al) x Ga 1-x ) 1-y In y ]P, the material of the cladding layers 5, 6 is [ (Al) u Ga 1-u ) 1-v In v ]P or AlInP, the waveguide layer 4 and the cladding layers 5 and 6 are made of different materials, the band gap width of the waveguide layer is smaller, the refractive index of the waveguide layer is larger, and the semiconductor substrate 7 is made of n-GaAs; and for example, a wavelength of 1300-1700nm [ (Al) x Ga 1-x ) 1- y In y ]As/[(Al x Ga 1-x ) 1-y In y ]In the As/InP system, the material of the active layer 3 is [ (Al) x Ga 1-x ) 1-y In y ]As quantum well, waveguide layer 4 is made of [ (Al) u Ga 1-u ) 1-v In v ]As, the cladding layers 5 and 6 are made of InP, and the semiconductor substrate 7 is made of n-InP; other GaAsP/[ (Al) with 750-900nm wavelength x Ga 1-x ) 1-y In y ]P/[(Al u Ga 1-u ) 1-v In v ]P/GaAs epitaxial system, in (Al) GaAs/(Al) with wavelength of 800-1100nm x Ga 1-x )As/(Al y Ga 1-y ) As/GaAs epitaxial system and GaAs/(Al) with wavelength of 800-870nm x Ga 1-x )As/(Al y Ga 1-y ) As/GaAs epitaxial system. The passivation layer can effectively passivate the semiconductor laser resonant cavity surface epitaxial material systems with various wave bands by adopting wet vulcanization, and the PCD can also deposit a wide-bandgap oxysulfide film on the vulcanized semiconductor laser resonant cavity surface epitaxial material systems.
The following description will be made of a specific example of the manufacturing method of the present application and the passivation film and the laser diode device manufactured by the method, and the specific description is as follows:
passivating by adopting a wet-process vulcanization reaction, carrying out the vulcanization reaction on the surface of the resonant cavity to form a sulfide film to serve as a passivation layer, and preparing the sulfide film by adopting a PCD method, wherein Zn (S) is firstly used 1-δ O δ ) Taking 0.2 ≧ delta > 0 as an example, taking the protective layer as a passivation layer, the solution of wet-process vulcanization and PCD is a sulfur-containing compound solution, the sulfur source thiosulfate in the solution can provide the sulfur required for the vulcanization reaction to form the passivation layer, and the thiosulfate also provides the Zn (S) for the subsequent PCD preparation 1-δ O δ ) A sulfur source for the protective layer.
First, the production of wet vulcanization and Zn (S) 1-δ O δ ) Preparing a solution of a protective layer, explaining a device for manufacturing a passivation film, explaining the passivation and Zn plating (S) for manufacturing the passivation layer by operating the bar resonant cavity surface 1-δ O δ ) And (5) a step of protecting the layer, and then manufacturing a laser diode device and testing the resistance of the COMD.
1) Preparing a solution for preparing a passivation film:
pure water is taken as a solvent, and the components are as follows:
zinc sulfate (ZnSO) 4 ) The concentration is 0.004M, and the zinc source in the coating is obtained;
sodium thiosulfate (Na) 2 S 2 O 3 ) The concentration is 0.1M, and the sulfur in the plating layer is sourced;
sodium citrate (Na) 3 C 6 H 5 O 7 ) The concentration is 0.01M, and citric acid and citrate can be formed after being dissolved in water and can be used as a complexing agent of zinc ions;
the solution preparation is kept at room temperature, the solvent is deionized water, the electrical impedance is greater than 18M omega cm, nitrogen with the purity of 99.9999 percent is introduced into the deionized water for 30 minutes before the solution preparation, and gas dissolved in the water, including oxygen, carbon dioxide and the like, can be brought out by nitrogen bubbles, so that the oxidation of thiosulfate radicals can be slowed down, the solution is more stable, and the service life is longer; then, respectively dissolving zinc sulfate, sodium citrate and sodium thiosulfate with specific weight in a small amount of deionized water, mixing a zinc sulfate solution and a sodium citrate solution, stirring the solution by using a ceramic magneton stirrer, then adding a sodium thiosulfate solution into the mixed solution of the zinc sulfate and the sodium citrate, stirring the mixed solution for 2 minutes, filling the solution into a volumetric flask, adding a small amount of water into the volumetric flask to reach a specific volume, uniformly mixing the solution to reach the components of the solution, and finally adjusting the pH value of the process solution to 5.7 by using concentrated sulfuric acid and an aqueous solution of sodium hydroxide to prepare for proper use.
2) Device for passivation film fabrication:
the apparatus of the process is shown in FIG. 5, the solution is placed in the quartz vessel of FIG. 5, the temperature of the solution can be raised by heating with a magnetic stirrer, the temperature of the solution is controlled at 30 ℃, and nitrogen is continuously introduced.
The ultraviolet light source adopts a XeI excimer lamp (eximer lamp) of 20W, the wavelength of a radiation main peak is 253nm, the ultraviolet light is converged on a resonant cavity surface (a front resonant cavity surface and a rear resonant cavity surface respectively) of the semiconductor laser device by using a converging lens, and the power density of the ultraviolet light at the position of the resonant cavity surface is about 100-300 mW/cm 2 (ii) a A baffle is arranged between the light source and the converging lens, the baffle controls whether ultraviolet light passes through or not, and the action and the interval time of the baffle are controlled by a computer; the design of quartz household utensils makes the preceding chamber surface of resonant cavity face and back chamber surface apart from the internal surface of quartz household utensils lateral wall about 3mm respectively, and whole devices of fig. 5 are placed in a dark box, can avoid ultraviolet ray to disperse and cause the injury to the human eye, also can prevent simultaneously that the ultraviolet ray of environment from shining solution, avoid the thiosulfate to decompose, keep solution stability and increase of service life.
3) The method comprises the following steps of (1) manufacturing a passivation film on a bar resonant cavity surface:
firstly, splitting a wafer on which a laser device is manufactured into bars in an atmospheric environment; secondly, clamping the bars by using a clamp made of polytetrafluoroethylene material, and simultaneously clamping a plurality of bars at one time to form parallel bar stacking; then immersing the bars into the solution shown in the figure 5 for vulcanization passivation (at the moment, the ultraviolet lamp is not started), wherein the passivation time is 5-30min; after the sulfuration passivation is finished, a passivation layer is formed on the resonant cavity surface, then, the ultraviolet light source is started, and the protective layer Zn (S) is carried out 1-δ O δ ) Plating. The shutter is switched on and off in a periodic process in which ultraviolet light is applied to the shutter during a periodThe passing time is 10-60s, the ultraviolet light is blocked for 10-600s, and a plurality of cycles are carried out, namely the total time of irradiating the ultraviolet light on the resonant cavity surface of the semiconductor laser device is 30-120 minutes, and the thickness of the zinc sulfide film can reach about 1-300 nm.
Through the sulfuration passivation and Zn (S) 1-δ O δ ) After the passivation film is manufactured, the bar is taken out and washed by deionized water, the solution is removed, and then the bar is dried by nitrogen.
In addition, the bar after the passivation film is formed may be heat treated to increase the light transmittance of the passivation layer, but the heat treatment temperature is not higher than the lowest temperature in the previous wafer process to avoid damaging the laser.
The subsequent bars can be additionally plated with optical film layers with required reflectivity on the front and rear resonant cavity surfaces according to the characteristic requirements of the semiconductor laser device, or further cut into single chips or arrays.
To obtain Zn (S) 1-δ O δ ) The above method is used to obtain Zn (S) 1-δ O δ ) The coating film is plated on a BK7 glass substrate, has high light transmittance, is measured by a transmission spectrum, and is calculated by Tauc plot to obtain a band gap width of about 3.6eV, which is higher than the energy of laser photons excited by the laser devices of the epitaxial systems, and meets the design requirement of the laser devices; in addition, the coating component is analyzed by a scanning electron microscope-energy spectrometer to obtain the oxygen content delta approximately equal to 0.04, namely the protective layer coating is Zn (S) 0.96 O 0.04 )。
Based on the above, the resonant cavity surface of the high-power laser bar with the wavelength of 1064nm is vulcanized and passivated and coated with Zn (S) 0.96 O 0.04 ) Protective layer, zn (S) 0.96 O 0.04 ) The thickness of the protective layer is about 30nm, then, optical film layers are respectively plated on the front and the rear resonant cavity surfaces by an electron beam evaporation method, the reflectivity of the optical film layers on the front and the rear resonant cavity surfaces is 5% and 99%, the laser output is mainly emitted from the front resonant cavity surface with the reflectivity of 5%, the laser emission power of the rear resonant cavity surface is very weak, the bar is split into a single laser chip, and the laser chip only has one laser twoAnd (3) pole tube, adhering the laser chip on the copper-coated aluminum nitride heat sink by solder, finally, bonding gold wire to complete simple packaging, and then carrying out characteristic test on the laser device. In order to verify the efficacy of the passivation film, similar laser devices are manufactured at the same time and are used as reference comparison benchmark, and the only difference is that the laser devices are Zn-free (S) 0.96 O 0.04 ) And a protective layer. FIG. 6 shows the results of laser output power-current tests of two laser devices, showing that there is no Zn (S) 0.96 O 0.04 ) The laser device of the protective layer generates COMD on the front resonant cavity surface when the current is increased to 19A, the laser device fails instantly, the laser output power is reduced to be almost zero, and on the other hand, the laser device has Zn (S) 0.96 O 0.04 ) The COMD happens only when the current of the laser device of the protective layer rises to 29A, the resistance capacity of the COMD is improved by about 50% compared with that of the COMD of the laser device of a reference comparative standard, in addition, the reliability of 20 laser devices which are simply packaged is tested, and no failure occurs within 3000 hours after aging and burning test at 70 ℃ and working current.
Another example is Mn (S) 1-δ O δ ) Substituted Zn (S) 1-δ O δ ) The material of the protective layer, the band gap width of the MnS bulk material is 3.1eV, and the band gap width is larger than the photon energy of most laser, so that the MnS bulk material is a good candidate. Similarly, zn (S) was prepared as described above 1-δ O δ ) Mn (S) is prepared by the same method as the protective layer material 1-δ O δ ) Coating film, wherein the solution is prepared from MnSO 4 Substituted ZnSO 4 Minor changes in other process parameters, results and Zn (S) 1-δ O δ ) The coating film was similar, but Mn (S) 1-δ O δ ) The transmittance was improved by heat treatment (nitrogen atmosphere, 10 minutes), and thereafter, a band gap width of about 3.4eV and a value of delta 0.07 were obtained, that is, the PCD coating was Mn (S) 0.93 O 0.07 ) The process and the coating are applied to the manufacture of a laser with the wavelength of 980nm, mn (S) according to the procedure for manufacturing the laser with the wavelength of 1064nm 0.93 O 0.07 ) The thickness of the protective layer is 15nm, the reflectivities of the optical film layers of the front and rear cavity surfaces are 3% and 99%, respectively, and the heat treatment is performed in a vacuum electron beam evaporation apparatus after the optical film layer is coated, with the result thatRelatively low resistance to COMD (S) 0.93 O 0.07 ) The protective layer is about 28% higher, again showing the superiority of the technology of the present application; meanwhile, this example also illustrates that, through the selection and substitution of metal ions, oxysulfide films with various band gap widths can be formed, and the oxysulfide film with the band gap width larger than the photon energy of the laser can be applied to the manufacture of semiconductor lasers as long as the principle that the band gap width of the oxysulfide is larger than the photon energy of the laser is satisfied.
Another embodiment is that the material of the protective layer is an alloy material of a wide band gap sulfur oxide: zn (S) doped with Al 1-δ O δ ) To (Zn) with 1-x Al x )(S 1-δ O δ ) And (4) showing. The preparation method is based on the Zn (S) 1-δ O δ ) The solution for vulcanizing passivation and protective layer plating comprises the following components:
zinc sulfate (ZnSO) 4 ) The concentration is 0.002M, and the zinc source in the plating layer is obtained;
aluminum sulfate (Al) 2 (SO 4 ) 3 ) The concentration is 0.002M, and the source of aluminum in the plating layer is;
hydrazine hydrate (hydrazine hydrate) ， (NH 2 ) 2 ·H 2 O) concentration of 0.04M, strong reducing agent for reducing oxygen content in the coating film;
ammonia water with concentration of 0.012M is used as complexing agent of zinc and aluminum ions;
sodium thiosulfate (Na) 2 S 2 O 3 ) The concentration is 0.1M, and the sources of sulfur in the PCD coating and the sulfuration passivation are selected;
the band gap width of the coating obtained by applying the solution is about 3.7eV, x is about 0.07, delta is about 0.02, namely the coating is (Zn) 0.93 Al 0.07 )(S 0.98 O 0.02 ) X-ray diffraction shows that the coating film is of a Wurtzite (Wurtzite) structure with a nano-scale crystal particle size; the process and the coating are applied to the manufacture of a laser with the wavelength of 640nm according to the procedure for manufacturing the laser with the wavelength of 1064nm, (Zn) 0.93 Al 0.07 )(S 0.98 O 0.02 ) The thickness of the protective layer is 25nm, and the optical film layers of the front resonant cavity surface and the rear resonant cavity surfaceThe reflectivities were 5% and 99%, respectively, with the result that the COMD resistance was less (Zn) 0.93 Al 0.07 )(S 0.98 O 0.02 ) The protective layer is higher than about 33%, in addition, 10 laser devices which are simply packaged are tested for reliability, and no failure is caused after the test of burning under the working current of 70 ℃ for 2600 hours, and the result shows the superiority and the application universality of the technology of the application again; this example also shows that the selection and addition of metal ion species, in combination with an appropriate metal ion complexing agent, can form oxysulfide alloy material thin films with various band gap widths, and can be applied to the fabrication of semiconductor lasers as long as the principle that the band gap width of oxysulfide is greater than the photon energy of laser is satisfied.
In all of the three examples above, thiosulfate was used as the sulfur source for sulfidizing passivation and plating of the protective layer of sulfur oxide, but in practice, other substances besides thiosulfate also exhibit the same effect, and include the following three types: thiosulfonate (R-S) 2 O 2 - R is a hydrocarbon group), thiophosphate (SPO) 3- ) Or dithiophosphoric acid radical (S) 2 PO 2 3- ) It may be a substance (salt, acid, ester, etc.) containing these three types of acid radicals in the chemical structural formula:
1) Thiosulfonate (R-S) 2 O 2 - ) Class (c): ethanethiosulfonate, methylthiosulfonate, thiobenzenesulfonate, 4-toluenesulthiosulfonate, p-toluenesulthiosulfonic acid, S-benzylmethanethiosulfonate, 2-aminoethanethiosulfonic acid, propargyl methanethiosulfonate, pentyl methanethiosulfonate, (3-sulfopropyl) methanethiosulfonate, 1,2-ethanediyldimethanethiosulfonate, 2-aminoethylmethanethiosulfonate, 5-aminopentylmethanthiosulfonate, S' - [1,2-ethanediylbis (oxy-2,1-ethanediyl)]A dimethane thiosulfonate;
2) Thiophosphate (SPO) 3- ) Class (c): thiophosphate, thiophosphate dimethyl ester salt, n-butyl thiophosphoric triamide, O-dimethyl thiophosphoric acid or salt, O, O-diethyl O-hydrogen thiophosphate, O-dimethyl thiophosphate, diethyl thiophosphoric potassium salt, O-diiso-phosphatePropyl thiophosphate, trimethyl thiophosphate, O, O, O-triethyl thiophosphate, O, O, O-triphenyl thiophosphate, 4-aminophenol thiophosphate, O, O-dimethyl thiophosphate, O, O-diethyl thiophosphate, N ', N' -trimethyl thiophosphoric triamide, ditolyl monothiophosphate, O-dimethyl-O- (2-ethylthioethyl) thiophosphate, O-2,4-dichlorophenyl-O, O-diethyl thiophosphate, diethyl 2-isopropyl-4-methyl-6-pyrimidinyl thiophosphate;
3) Dithiophosphate radical (S) 2 PO 2 3- ) Class (ii): dithiophosphate, diisobutyldithiophosphate, O-m-tolyl O-p-tolyl dithiophosphate, xylenol dithiophosphate, dimethyldithiophosphate, O-bis (1-methylpropyl) dithiophosphate, dialkyldithiophosphate, O-dibutyldithiophosphate, O-bis (1,3-dimethylbutyl) dithiophosphate, tolyldithiophosphate, diethyl dithiophosphate, diisopropyl dithiophosphate, dithiophosphoric acid-O, O-bis (1-methylethyl) ester, O-ethyl-S-propyl dithiophosphate, O-dimethyldithiophosphate, O '-diethyldithiophosphate, O-diethyl-S-propyl dithiophosphate, dimethoxydithiophosphoric acid methyl acetate, O-phenyldithiophosphate, dimethylphenol dithiophosphate, di (O, O-diisodecyl dithiophosphate-S, S') -salt, di (tetrapropylphenol) dithiophosphate, di (O, O-didodecyl) dithiophosphate-S, S,) salt, di [ O, O-di (dodecylphenyl) dithiophosphate]-S, S-salts, diethyl dithiophosphate ammonium salts, (O, O-isobutyl and pentyl) dithiophosphate salts, O-diisooctyl dithiophosphate salts, (T-4) -di [ O-hexyl O- (6-methylheptyl) dithiophosphate]Salts, bis [ O- (2-ethylhexyl) -O- (2-methylpropyl) dithiophosphoric acid]Salts, (T-4) -bis (O, O-bis (2-ethylhexyl) dithiophosphoric acid-S, S) salts, mixed salts of dithiophosphoric acid-O, O-bis (hexyl and isobutyl) esters, and (T-4) -bis [ O, O-bis (1-methylethyl) dithiophosphoric acid-S, S']Salt, (T-4) bis [ O, O-bis (1,3-dimethylbutyl) dithiophosphoric acid-S-S]Salts, dithiophosphoric acid-O, O-bis (sec-butyl and 1,3-dimethylbutyl) mixed ester salts, dibutyl dipropyloxydithiophosphate, O-didodecyldithiophosphate, O-ethyl O- (4-methylthiophenyl) S-propyl dithiophosphate, S- (dimethylformamidomethyl) O, O-dimethyldithiophosphate;
the salts include metal salts and ammonium salts.
It can be concluded from the above three embodiments that the ability of the semiconductor laser device to resist COMD can be effectively improved by performing PCD plating to form a wide bandgap oxysulfide protective film on the cavity surface of the semiconductor laser device after wet-sulfidation, and thus the service life of the semiconductor laser device is ensured, and besides the uniqueness of the process, the superiority of the passivation film material and structure is also shown; in addition, the passivation film material and the structure can also be manufactured by other methods, for example, the passivation layer can be generated by plasma vulcanization, and then a sulfur oxide protective layer is plated by a plasma technology, but the process is slightly complicated, the complexity of the process and the volatilization risk of the sulfur of the passivation layer are increased by the method, so that the laser performance is reduced; another method is to form a passivation layer by wet vulcanization, and then to form a sulfur oxide as a passivation layer by CBD or electroplating. The combination of these methods theoretically produces a passivation film very similar to the present application, but both the process simplicity and cost are inferior to the techniques disclosed in the present application.
In the embodiment of the application, after a passivation layer is formed on the resonant cavity surface of the semiconductor laser device, a protective layer is covered on the passivation layer, and the protective layer is made of a wide-bandgap oxysulfide material, so that the passivation effect failure caused by oxidation or volatilization of the passivation layer on the resonant cavity surface can be prevented. The effect of the resonant cavity surface passivation film of the semiconductor laser device of the present application mainly includes two aspects, namely, the passivation effect and the stability thereof. The wide-band-gap oxysulfide material is selected as the protective layer material, so that the protective layer material can be prevented from absorbing laser photons, the passivation layer material is prevented from being oxidized or volatilized, the passivation layer material is prevented from losing efficacy, the COMD resistance of the semiconductor laser device is improved, the resonant cavity surface passivation film can be effective for a long time in this way, the reliability of the semiconductor laser device can be guaranteed, and the service life of the semiconductor laser device is prolonged. Furthermore, the passivation layer and the protective layer are formed in the same sulfur-containing compound solution, so that the manufacturing process can be simplified, and the manufacturing efficiency of the passive film of the resonant cavity surface can be improved.
In summary, the passivation technology for the resonant cavity surface of the semiconductor laser device combines the wet vulcanization passivation and the photochemical deposition method for the wide-gap oxysulfide film, wherein PCD is a region selective deposition, and the oxysulfide film formed by the PCD only occurs in the region irradiated by ultraviolet light, i.e., the resonant cavity surface of the semiconductor laser device. Although the embodiment of the application discloses the use of the ultraviolet lamp, the laser with the ultraviolet wavelength has the same effect, but the price of the laser device with the ultraviolet wavelength is much higher than that of the ultraviolet lamp, so that the production cost is unfavorable.
The above description is only an embodiment of the present application, and is not intended to limit the scope of the present application, and all equivalent structures or equivalent processes performed by the present application and the contents of the attached drawings, which are directly or indirectly applied to other related technical fields, are also included in the scope of the present application.
Claims (18)
1. A resonator surface passivation film of a semiconductor laser device, comprising:
a passivation layer covering the resonant cavity surface of the semiconductor laser device;
the protective layer covers the passivation layer, and the material of the protective layer is a wide-band-gap oxysulfide material;
the passivation layer and the protective layer are manufactured and formed in the same sulfur-containing compound solution.
2. The passive film according to claim 1, wherein the passivation layer is a sulfur-containing film formed by reacting a semiconductor epitaxial material of a cavity surface of the semiconductor laser device with a sulfur-containing compound; the thickness of the passivation layer is several to tens of atomic layer thickness.
3. The resonator surface passivation film of claim 1, wherein the protective layer has a thickness of 1-800nm; the protective layer is a component or all of the subsequent resonator surface optical film.
4. The resonant cavity surface passivation film of claim 1, wherein the wide bandgap is a bandgap width of sulfur oxide that is greater than a photon energy of a laser.
5. The resonant cavity surface passivation film of claim 1, wherein the wide bandgap sulfur oxide material comprises: zn (S) 1-δ O δ )、Cd(S 1-δ O δ )、Mg(S 1-δ O δ )、Ca(S 1-δ O δ )、Sr(S 1-δ O δ )、Ba(S 1-δ O δ )、Al 2 (S 1-δ O δ ) 3 、Ga 2 (S 1-δ O δ ) 3 、In 2 (S 1-δ O δ ) 3 、Sn(S 1-δ O δ ) 2 、Sn(S 1-δ O δ )、Sb 2 (S 1-δ O δ ) 3 、Bi 2 (S 1-δ O δ ) 3 、Mn(S 1-δ O δ ) Wherein the range of δ is: delta is more than 0.2 and more than 0.
6. The passive film according to claim 1, wherein the material of the protective layer is a mixture of wide band gap sulfur oxide materials containing at least two or more metal ions forming two or more sulfur oxides.
7. The resonator facet passivation film according to claim 6, characterized in that the mixture of wide band gap sulfur oxide materials includes the following sulfur oxides Zn (S) 1-δ O δ )、Cd(S 1-δ O δ )、Mg(S 1-δ O δ )、Ca(S 1-δ O δ )、Sr(S 1-δ O δ )、Ba(S 1-δ O δ )、Al 2 (S 1-δ O δ ) 3 、Ga 2 (S 1-δ O δ ) 3 、In 2 (S 1-δ O δ ) 3 、Sn(S 1-δ O δ ) 2 、Sn(S 1-δ O δ )、Sb 2 (S 1-δ O δ ) 3 、Bi 2 (S 1-δ O δ ) 3 、Mn(S 1-δ O δ ) Wherein δ is in the range of: 0.2 is more than or equal to delta and more than 0.
8. The resonator surface passivation film according to claim 1, wherein the material of the protective layer is an alloy material of a wide-bandgap sulfur oxide, which contains at least two or more metal ions to form a single kind of sulfur oxide.
9. The resonator face passivation film of claim 8, wherein the alloy material of the wide band gap sulfur oxide includes: (Zn) 1-x Cd x )(S 1-δ O δ )、(Mg 1-x Ca x )(S 1-δ O δ )、(Zn 1-x Ca x )(S 1-δ O δ )、(Ca 1-x Sr x )(S 1-δ O δ )、(Mg 1-x-y Ca x Ba y )+(S 1-δ O δ )、(Al 1-x Ga x ) 2 (S 1-δ O δ ) 3 、(Zn 1-x Al x )(S 1-δ O δ )、(Zn 1-x Ga x )(S 1-δ O δ )、(Zn 1- x Mn x )(S 1-δ O δ )、(Zn 1-x-y Cd x Mn y )(S 1-δ O δ ) Wherein the ranges of x and y are: 1 > x, y > 0, said δ being in the range: delta is more than 0.2 and more than 0.
10. A semiconductor laser device comprising a resonator surface passivation film, said resonator surface passivation film being as claimed in any one of claims 1 to 9.
11. A method for manufacturing a resonant cavity surface passivation film of a semiconductor laser device is characterized by comprising the following steps:
covering a thin film of a vulcanization passivation layer on the resonant cavity surface of the semiconductor laser device;
and covering a protective layer film on the passivation layer by adopting a photochemical deposition method, wherein the protective layer is made of a wide-band-gap oxysulfide material.
Wherein, the passivation layer and the protective layer are manufactured and formed in the same sulfur-containing compound solution.
12. The method of claim 11, wherein the step of covering the cavity surface of the semiconductor laser device with a thin film of a sulfide passivation layer comprises:
immersing the prepared bar into the sulfur-containing compound solution, and carrying out wet vulcanization on the resonant cavity surface of the semiconductor laser device to form the passivation layer; the wet vulcanization process is carried out without ultraviolet irradiation, and after the wet vulcanization is finished, the thickness of the passivation layer is several atomic layers to dozens of atomic layers;
the method for covering a protective layer on the passivation layer by adopting a photochemical deposition method comprises the following steps:
and starting an ultraviolet light source to perform photochemical deposition reaction, and covering a protective layer film on the passivation layer.
13. The method of manufacturing according to claim 11,
the sulfur-containing ions in the sulfur-containing compound solution used for manufacturing the passive film of the resonant cavity surface contain thiosulfate (S) in the chemical structural formula 2 O 3 2- ) Thiosulfonate (R-S) 2 O 2 - ) Thiophosphate (SPO) 3- ) Or dithiophosphoric acid (S) 2 PO 2 3- ) The solvent of the sulfur-containing compound solution is water or an organic solvent, or a mixed solution of water and an organic solvent.
14. The method of claim 12, wherein the sulfur compound solution uses a raw material comprising at least one of:
1) Thiosulfate radical (S) 2 O 3 2- ) Class (c): thiosulfate or thiosulfuric acid;
2) Thiosulfonate (R-S) 2 O 2 - ) Class (c): ethanethiosulfonate, methylthiosulfonate, thiobenzenesulfonate, 4-toluenesulthiosulfonate, p-toluenesulthiosulfonic acid, S-benzylmethanethiosulfonate, 2-aminoethanethiosulfonic acid, propargyl methanethiosulfonate, pentyl methanethiosulfonate, (3-sulfopropyl) methanethiosulfonate, 1,2-ethanediyldimethanethiosulfonate, 2-aminoethylmethanethiosulfonate, 5-aminopentylmethanthiosulfonate, S' - [1,2-ethanediylbis (oxy-2,1-ethanediyl)]A dimethane thiosulfonate;
3) Thiophosphate (SPO) 3- ) Class (c): thiophosphates, thiophosphoric acid dimethyl ester salts, n-butyl thiophosphoric triamides, O, O-dimethyl thiophosphoric acid or salts, O, O-diethyl-O-hydrogen thiophosphate, O, O-dimethyl thiophosphate, diethyl thiophosphoric potassium salt, O, O-diisopropyl thiophosphate, trimethyl thiophosphate, O, O, O-triethyl thiophosphate, O, O, O-triphenyl thiophosphoric acidEsters, 4-aminophenol thiophosphate, O-dimethyl thiophosphate, O-diethyl thiophosphate, N', N "-trimethyl thiophosphoric triamide, ditolyl monothiophosphate, O-dimethyl-O- (2-ethylthioethyl) thiophosphate, O-2,4-dichlorophenyl-O, O-diethyl thiophosphate, diethyl 2-isopropyl-4-methyl-6-pyrimidinyl thiophosphate;
4) Dithiophosphate radical (S) 2 PO 2 3- ) Class (ii): dithiophosphates, diisobutyldithiophosphates, O-m-tolyl O-p-tolyl dithiophosphates, xylenyldithiophosphates, dimethyldithiophosphates, O-dimethyldithiophosphate salts, O-bis (1-methylpropyl) dithiophosphate salts, dialkyldithiophosphates, O-dibutyldithiophosphates, O-bis (1,3-dimethylbutyl) dithiophosphates, tolyldithiophosphates, diethyl dithiophosphates, diisopropyl dithiophosphates, dithiophosphoric acid-O, O-bis (1-methylethyl) ester, O-ethyl-S-propyl dithiophosphate, O-dimethyldithiophosphate, O '-diethyldithiophosphate, O-diethyl-S-propyl dithiophosphate, dimethoxydithiophosphoric acid methyl acetate, O-phenyldithiophosphate, dimethylphenol dithiophosphate, di (O, O-diisodecyl dithiophosphate-S, S') -salt, di (tetrapropylphenol) dithiophosphate, di (O, O-didodecyl) dithiophosphate-S, S,) salt, di [ O, O-di (dodecylphenyl) dithiophosphate]-S, S-salts, ammonium diethyldithiophosphates, (O, O-isobutyl and pentyl) dithiophosphoric acid ester salts, O-diisooctyl dithiophosphates, (T-4) -di [ O-hexyl O- (6-methylheptyl) dithiophosphoric acid]Salts, di [ O- (2-ethylhexyl) -O- (2-methylpropyl) dithiophosphoric acid]Salts, (T-4) -bis (O, O-bis (2-ethylhexyl) dithiophosphoric acid-S, S) salts, mixed salts of dithiophosphoric acid-O, O-bis (hexyl and isobutyl) esters, and (T-4) -bis [ O, O-bis (1-methylethyl) dithiophosphoric acid-S, S']Salt, (T-4) bis [ O, O-bis (1,3-dimethylbutyl) dithiophosphoric acid-S]Salts, O-bis (sec-butyl and 1,3-dimethylbutyl) dithiophosphoric acid mixed ester salts, dipropyloxydithiophosphoric acidDibutyl succinate, O-didodecyl hydrogen dithiophosphate, O-ethyl O- (4-methylthiophenyl) S-propyl dithiophosphate, S- (dimethylformamidomethyl) O, O-dimethyldithiophosphate;
the salts include metal salts and ammonium salts.
15. The method of manufacturing according to claim 11,
the sulfur-containing compound solution used for manufacturing the passive film of the resonant cavity surface contains ions or complex ions of the following elements: at least one of zinc, cadmium, magnesium, calcium, strontium, barium, aluminum, gallium, indium, tin, antimony, bismuth or manganese ions or complex ions as a source of the cationic component in the protective layer.
16. The method of claim 11, wherein said wide bandgap sulfur oxide material has a bandgap width greater than the laser photon energy; the photochemical deposition method is to irradiate the resonant cavity surface of the semiconductor laser device by adopting ultraviolet light, and the ultraviolet light irradiation mode is continuous irradiation or intermittent irradiation.
17. The method of claim 16, wherein the ultraviolet light has a wavelength of less than 400nm.
18. The method of claim 16, wherein the source of ultraviolet light comprises: ar (Ar) 2 *、Kr 2 *、Xe 2 *、F 2 *、Cl 2 *、Br 2 *、I 2 * NeF, arF, arCl, arBr, krF, krCl, krBr, krI, xeF, xeCl, xeBr, xeI, excimer lamp, mercury lamp, xenon mercury lamp, deuterium arc lamp, hydrogen arc lamp, xenon-antimony arc lamp, carbon arc lamp, metal halide lamp, UV-B ultraviolet lamp, ultraviolet light emitting diode, and ultraviolet laser.
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| CN117096724B (en) * | 2023-10-20 | 2024-02-06 | 度亘核芯光电技术(苏州)有限公司 | Cavity surface cleaning and passivating method |
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