CN104862784A - Method for manufacturing monocrystalline film with near stoichiometric ratio - Google Patents
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Abstract
The invention discloses a method for manufacturing a monocrystalline film with a near stoichiometric ratio. The method comprises steps: ions are injected into a surface of an original substrate through an ion injection method, and therefore a thin film layer, a separation layer and a residual layer are formed in the original substrate; an object substrate contacts with the thin film layer of the original substrate, therefore the original substrate and the object substrate are bonded together through a chip bonding method to form a bonding body; the bonding body is heated and thus the thin film is separated from the residual layer; after the thin film layer is separated from the residual layer, the thin film layer is heated at a temperature of 200-700 DEG C in a predetermined container loaded with diffusion agents, and the diffusion agents comprise at least one of lithium oxide and lithium nitrate. Through the method, the problem that a monocrystalline film lacks in a lithium phase can be avoided effectively, and a monocrystalline film with a nanoscale thickness and with a uniform film thickness and with components with a near ideal stoichiometric ratio is manufactured.
Description
Technical field
The present invention relates to a kind of method manufacturing monocrystal thin films, specifically, relate to a kind of nanometer grade thickness, uniform film thickness, component close to the manufacture method of the monocrystal thin films of ideal stoichiometric ratio.
Background technology
Lithium niobate monocrystal film and monocrystalline lithium tantalate film (hereinafter referred to as film or monocrystal thin films) have been widely used at field tools such as optical signal prosessing, information storage and electron devices, it can as substrate material, may be used for making high frequency, high bandwidth, high integration, Large Copacity, the optoelectronics device of highly sensitive, reduce power consumption and stable performance and integrated optical device, such as, wave filter, waveguide modulator, optical waveguide switch, spatial light modulator, optical frequency doubler, surface acoustic wave producer, infrared eye and ferroelectric storage etc.The most frequently used lithium niobate monocrystal thin-film material generally can be divided into three kinds of structures, and wherein, the first structure is followed successively by lithium niobate monocrystal film, silicon dioxide layer and lithium niobate substrate from top to bottom; The second structure is followed successively by lithium niobate monocrystal film, electrode, silicon dioxide layer and lithium niobate substrate from top to bottom; The third structure is followed successively by lithium niobate monocrystal film, silicon dioxide layer, electrode and lithium niobate substrate from top to bottom.The thickness of lithium niobate monocrystal film is generally between 50 nanometer to 3000 nanometers, and the thickness of silicon dioxide layer is generally between 200 nanometer to 3000 nanometers.Monocrystalline lithium tantalate film has the structure identical with lithium niobate monocrystal film, therefore does not repeat them here.
In the process making lithium niobate monocrystal film, need experience annealing process to strengthen linkage force and to eliminate the ion implantation damage caused, thus improve the yield rate of finished films.Usually, annealing temperature needs to control between 200 DEG C to 900 DEG C.For lithium niobate monocrystal film, when annealing temperature is more than 300 DEG C, lithium niobate monocrystal film there will be phase transformation, even there will be the phenomenon of decomposed, namely forms LiNb
3o
8mutually or with Lithium Oxide 98min (Li
2o) form diffuses out lithium niobate monocrystal film, thus the rich niobium structure causing lithium niobate monocrystal film to become heterogeneous, can be regarded as the mixture (LiNbO of Lithium niobium trioxide and Niobium Pentxoxide
3+ Nb
2o
5).
When there being rich niobium structure to exist in lithium niobate monocrystal film, optical property and the electrical properties of lithium niobate monocrystal film can be had a strong impact on, especially for the lithium niobate monocrystal film of containing metal electrode.When metal electrode contacts with LiNbO_3 film layer, metal electrode and Lithium niobium trioxide react near contact surface, make the situation of the lithium niobate monocrystal film of containing metal electrode disappearance Lithium Oxide 98min more serious.When lithium niobate monocrystal film disappearance Lithium Oxide 98min, the performance of its device can be had a strong impact on, index is fallen flat, can not use even at all.
Summary of the invention
One object of the present invention is to provide a kind of method manufacturing the monocrystal thin films of near stoichiometric proportion, and described method can produce nanometer grade thickness, uniform film thickness, component close to the monocrystal thin films of ideal stoichiometric ratio.
The invention provides a kind of method manufacturing the monocrystal thin films of near stoichiometric proportion, described method comprises: by ion implantation by the ion implantation surface to original substrate, thus in original substrate, form thin film layer, separating layer and remaining matter layer, wherein, thin film layer is positioned at the surface of original substrate, separating layer is between thin film layer and remaining matter layer, and the ion distribution of injection is in separating layer; Make the thin film layer of target base plate and original substrate, and then utilize wafer bonding method original substrate and target base plate to be bonded together, to form bonding body; Para-linkage body heats, and thin film layer is separated with remaining matter layer; After thin film layer is separated with remaining matter layer, heat in the predetermined container that diffusant is housed with the temperature of 200 DEG C ~ 700 DEG C to thin film layer, wherein, diffusant comprises at least one in Lithium Oxide 98min and lithium nitrate.
According to embodiments of the invention, diffusant is the mixture of Lithium Oxide 98min or Lithium Oxide 98min and Lithium niobium trioxide.
According to embodiments of the invention, in the step that thin film layer is heated, pass into oxygen to predetermined container, make thin film layer be heated to make Lithium Oxide 98min to be diffused in thin film layer at the temperature of 200 DEG C ~ 700 DEG C.
According to embodiments of the invention, described predetermined container comprises: for placing the first container of diffusant, one end of the first container is provided with inlet mouth; For placing the second container of film, one end of second container is provided with air outlet; For the first container being connected to the pipeline of second container; To the primary heater that the first container heats; And to the secondary heater that second container heats.
According to embodiments of the invention, diffusant is the mixture of at least one in lithium nitrate or SODIUMNITRATE, saltpetre and lithium nitrate.
According to embodiments of the invention, in the step that thin film layer is heated, thin film layer is immersed in and is in the diffusant of molten state, make thin film layer be heated to make lithium ion to be diffused in thin film layer at the temperature of 200 DEG C ~ 700 DEG C.
According to embodiments of the invention, described method is also included in after para-linkage body carries out the step heated and before the step heated thin film layer, under the condition of 300 DEG C ~ 600 DEG C, carry out anneal to thin film layer.
According to embodiments of the invention, described method is carried out surface finish process to thin film layer, and/or after the step heated thin film layer, is carried out surface finish process to thin film layer before being also included in the step to thin film layer heating.
According to embodiments of the invention, target base plate be coated with silicon dioxide layer or be coated with electrode layer and silicon dioxide layer, and making the thin film layer of silicon dioxide layer and original substrate, to form bonding body; Or on the surface of the thin film layer of original substrate, be coated with electrode layer and silicon dioxide layer, and silicon dioxide layer is contacted with target base plate, to form bonding body.
According to embodiments of the invention, carry out in the step heated at para-linkage body, under vacuum or be greater than 1 normal atmosphere and para-linkage body carries out heating thin film layer is separated with remaining matter layer under being less than 300 atmospheric atmosphere.
According to embodiments of the invention, described film is lithium niobate monocrystal film or monocrystalline lithium tantalate film.
According to the method for the monocrystal thin films of manufacture near stoichiometric proportion of the present invention, film effectively can be avoided to lack the problem of lithium phase, produce nanometer grade thickness, uniform film thickness, component close to the monocrystal thin films of ideal stoichiometric ratio.
Accompanying drawing explanation
By below in conjunction with exemplarily illustrating the description that the accompanying drawing of an example carries out, above and other object of the present invention and feature will become apparent, wherein:
Fig. 1 is the FB(flow block) of the method that manufacture monocrystal thin films of the present invention is shown;
Fig. 2 is the structural representation that dispersion device is shown.
Embodiment
Be described in detail below in conjunction with the method for accompanying drawing to the monocrystal thin films of manufacture near stoichiometric proportion of the present invention.
The invention provides a kind of method manufacturing the monocrystal thin films of near stoichiometric proportion, as shown in Figure 1, method of the present invention comprises the steps: by ion implantation, by the surface imp lantation of ion facing to original substrate, forms thin film layer, separating layer and remaining matter layer; Original substrate and target base plate bonding are formed bonding body; Para-linkage body carries out heating and thin film layer is separated with remaining matter layer; And thin film layer is transferred in target base plate, to film heating in dispersion device.
Specifically, passing through ion implantation, by the surface imp lantation of ion facing to original substrate, formed in the step of thin film layer, separating layer and remaining matter layer, use ion implantation, the upper surface of ion (can be molion) facing to original substrate is injected, form separating layer, original substrate is divided into upper and lower twoth district by separating layer: a region being the overwhelming majority and injecting the equal process of ion, is called thin film layer; Another be the overwhelming majority inject ion without region, be called remaining matter layer.The thickness of thin film layer is decided (such as, helium ion energy can be 10keV ~ 2000keV, and the thickness of the thin film layer corresponding with this helium ion energy is between 60 nanometer to 4500 nanometers) by ion implantation energy.Wherein, the ion implantation that ion implantation can comprise conventional ion implanters injection method, plasma body soaks ion implantation and adopts the segmentation of different implantation temperature to inject, wherein, the ion injected in ion implantation can be at least one of hydrogen ion and helium ion.
The object of carrying out this ion implantation is in order to by a large amount of ion implantation top layers to original substrate, injection ion in separating layer plays pendulum in original substrate, inject ion and embed lattice imperfection, produce volumetric strain, cause separating layer to become area of stress concentration, thus make the weak mechanical strength of original substrate part near separating layer.
Original substrate and target base plate bonding being formed in the step of bonding body, utilize wafer bonding method, original substrate and target base plate are bonded together, form bonding body.Wherein, insulating layer coating (such as, SiO can be coated with on the surface of target base plate
2), this insulation layer is combined face-to-face with the thin film layer of original substrate, then carries out bonding, be followed successively by thin film layer, silicon dioxide layer and target base plate from top to bottom to make the membrane structure of making.Also can on the surface of target base plate electrode coated layer (such as, metal electrode) and insulation layer (such as, SiO
2), insulation layer is combined face-to-face with the thin film layer of original substrate, then carries out bonding, be followed successively by thin film layer, insulation layer, electrode layer and target base plate from top to bottom to make the membrane structure of making.Electrode layer and insulation layer (such as, SiO can also be coated with on the surface of the thin film layer of original substrate
2), insulation layer is combined face-to-face with target base plate, then carries out bonding, be followed successively by thin film layer, electrode layer, insulation layer and target base plate from top to bottom to make the membrane structure of making.
Wafer bonding method can be selected from the one in Direct Bonding method, anode linkage method, low-temperature bonding method, vacuum bonding method, plasma strengthening bonding method and bonding bonding method etc.
Carry out heating at para-linkage body in the step that thin film layer is separated with remaining matter layer, bonding body is placed in heating container, is then warming up to 150 DEG C ~ 300 DEG C, in the process heated up, the ion injected can become gas molecule or atom, form much small bubble, along with the prolongation of heat-up time or the rising of Heating temperature, bubble can get more and more, volume also increases gradually, finally, bubble phase connects, and thin film layer is separated with remaining matter layer.
In another embodiment of the invention, para-linkage body heats the step making it be separated and also can be greater than 1 normal atmosphere and under being less than 300 atmospheric atmosphere or carry out under vacuum condition.
Transfer in target base plate at thin film layer, in the step of film heating in dispersion device, after thin film layer is separated with remaining matter layer with target base plate, thin film layer has been transferred in target base plate, forms film.Being placed in by film is equipped with in the dispersion device of diffusant, under the condition of 200 DEG C ~ 700 DEG C, be heated to certain hour to film.
Diffusant comprises at least one in Lithium Oxide 98min and lithium nitrate.Being placed in by film is equipped with in the dispersion device of diffusant, under the condition of 200 DEG C ~ 700 DEG C, heating is carried out less than 100 hours to film, thus make the lithium had in the diffusant of high partial potential be diffused in the film with low partial potential mutually, avoid the phenomenon of film disappearance lithium phase, make component in film close to ideal stoichiometric ratio.
In one embodiment of the invention, diffusant can be the mixture of at least one in lithium nitrate or SODIUMNITRATE, saltpetre and lithium nitrate.In order to make the lithium ion in diffusant be diffused into more fully in film, preferably, certain hour can be heated to thin film dipped in the diffusant being in molten state.
In another embodiment of the present invention, diffusant can be the mixture of Lithium Oxide 98min or Lithium Oxide 98min and Lithium niobium trioxide.In the dispersion device of mixture that Lithium Oxide 98min or Lithium Oxide 98min and Lithium niobium trioxide are housed, heat Lithium Oxide 98min is diffused in film to film.Wherein, in order to make the Lithium Oxide 98min in diffusant to be diffused in film better, preferably, when film being heated under the condition of 200 DEG C ~ 700 DEG C, oxygen can be passed in dispersion device.
In an embodiment of the present invention, in order to make the Lithium Oxide 98min in diffusant to be diffused in film fully, as shown in Figure 2, dispersion device can comprise the first container 10 for placing diffusant, and one end of the first container 10 is provided with inlet mouth 11; For placing the second container 20 of film, one end of second container 20 is provided with air outlet 21; For the first container 10 being connected to the pipeline 30 of second container 20; The primary heater 40 that first container 10 is heated and the secondary heater 50 that second container 20 is heated.In order to prevent entering into the condensed on inner walls of the diffusant in second container 20 at pipeline 30, dispersion device also can comprise the 3rd well heater 60 heated pipeline 30.
When adopting above-mentioned dispersion device to heat to make Lithium Oxide 98min be diffused in film to film, diffusant (such as, the mixture of Lithium Oxide 98min or Lithium Oxide 98min and Lithium niobium trioxide) can be placed in the first container 10; Film is placed in second container 20; The temperature of primary heater 40 is controlled to 400 DEG C ~ 1200 DEG C, the temperature of secondary heater 50 is controlled to 200 DEG C ~ 700 DEG C; In the first container 10, pass into oxygen by inlet mouth 11, oxygen carries Lithium Oxide 98min steam and enters in second container 20, is diffused in film, and is flowed out by the air outlet 21 of second container 20.
In addition, in order to provide production efficiency, temperature in the first container 10 of placement diffusant can be made higher than the temperature in second container 20, thus make the saturated vapor pressure of Lithium Oxide 98min higher, the concentration entered in second container 20 is comparatively large, is conducive to Lithium Oxide 98min diffusion in the film.In this way, diffusion time can be shortened to 1 little of 30 hours.
In another embodiment of the invention, in order to strengthen linkage force and eliminate the ion implantation damage caused, also after the step of para-linkage body heating and before the step to film heating, under the condition of 300 DEG C to 600 DEG C, anneal can be carried out to film.
Method of the present invention also comprises the step of film being carried out to polished finish, this step can be selected before the step to film heating, surface finish process is carried out to thin film layer, or select after the step to film heating, surface finish process is carried out to thin film layer, also or select before the step to film heating and after the step to film heating, all surface finish process is carried out to thin film layer.
The monocrystal thin films of method manufacture of the present invention can be lithium niobate monocrystal film or monocrystalline lithium tantalate film.
The method of the monocrystal thin films of manufacture near stoichiometric proportion of the present invention, compared with manufacturing the method for the lithium niobate crystal chip of near stoichiometric proportion with traditional gas phase transmission balance method (VTE), there is gross differences: gas phase transmission balance method is the method for the compensation that the Lithium Oxide 98min deficient phenomena of a kind of lithium niobate crystal chip larger to thickness (thickness is greatly about 0.5 millimeter) carries out.The comparatively large and spread coefficient of diffusate and the diffusion temperature exponentially relation of thickness due to lithium niobate crystal chip, therefore, the diffusion temperature needs of traditional gas phase transmission balance method control more than 1000 DEG C.At this temperature, the vapour pressure of Lithium Oxide 98min is very high, the Lithium Oxide 98min of excessive concentrations can react with lithium niobate crystal chip surface, cause corrosion, so, the polycrystalline Lithium niobium trioxide pottery being rich in Lithium Oxide 98min generally can be selected as diffusant, but this diffusant preparation process is complicated, and needs diffusion time 100 hours guarantee Lithium Oxide 98mins to spread on lithium niobate crystal chip evenly.But for lithium niobate monocrystal film or monocrystalline lithium tantalate film, if diffusion temperature is higher than 700 DEG C, following problem can be there is.On the one hand, lithium niobate monocrystal film or monocrystalline lithium tantalate film generally include silicon dioxide layer, and because silicon-dioxide is different from the thermal expansivity of Lithium niobium trioxide, too high temperature can make film inside have larger internal stress, causes film deteriorates; On the other hand, lithium niobate monocrystal film or monocrystalline lithium tantalate film generally include electrode, and too high temperature can make electrode and the material around it easily chemical reaction occur, and produce impurity phase, even cause electrode melting; Again on the one hand, when being heated to 700 DEG C ~ 900 DEG C, phase transformation and the thermolysis of lithium niobate monocrystal film or monocrystalline lithium tantalate film can be aggravated, a large amount of Lithium Oxide 98mins can diffuse out from film, even if in the environment being rich in Lithium Oxide 98min, because the reason such as thermo parameters method and air flow method can cause Lithium Oxide 98min compensation uneven, finally cause the component skewness of lithium niobate monocrystal film or monocrystalline lithium tantalate film.Therefore, traditional gas phase transmission balance method is not suitable for prepares lithium niobate monocrystal film or monocrystalline lithium tantalate film.
And adopt the method for manufacture film of the present invention, can make and obtain the film of thickness in tens nanometer to three thousand nanometers, and this film is heated under the condition of low temperature (200 DEG C ~ 700 DEG C) 1 little of 60 hours, lithium phase (Lithium Oxide 98min or lithium ion) can be made to be diffused in film.In addition, adopt dispersion device of the present invention, can be shortened to 1 hour ~ 30 hours diffusion time, thus improve production efficiency.Therefore, the method for manufacture film of the present invention, can avoid film to lack the problem of lithium phase effectively, produces nanometer grade thickness, uniform film thickness, component close to the film of ideal stoichiometric ratio.
Illustrate that the present invention makes the detailed process of film to make lithium niobate monocrystal film below.
Embodiment 1
Original substrate is lithium niobate crystal chip, is 4 × 10 through overtreatment
16ions/cm
2helium ion (He
1+) inject, helium ion energy is 230keV.
Target base plate is lithium niobate crystal chip, utilizes plasma enhanced chemical vapor deposition method to deposit layer of silicon dioxide in target base plate, and utilizes chemical mechanical milling method that silicon dioxide layer is polished to 2 microns.
Utilize Direct Bonding method, the silicon dioxide layer of target base plate and original substrate are carried out bonding to form bonding body; Bonding body is heated to 220 DEG C, and keeps 10 hours at such a temperature, bonding body is separated and makes film.
The film obtained and Lithium Oxide 98min powder (solid) are put into encloses container heat, surrounding atmosphere is oxygen (O
2), temperature is 500 DEG C, and the time is 50 hours, takes out after film cooling.
Finally, polishing is carried out to the surface of film, obtains lithium niobate monocrystal film.
Now the very optical index of lithium niobate monocrystal film is lower than 2.202 (wavelength is 633 nanometers).In addition, the atomic ratio of lithium and niobium reaches more than 0.95:1, and this shows that the component of lithium niobate monocrystal film compares 1:1 close to ideal stoichiometric.
Embodiment 2
Original substrate is lithium niobate crystal chip, is 4 × 10 through overtreatment
16ions/cm
2helium ion (He
1+) inject, helium ion energy is 1000keV.
Target base plate is lithium niobate crystal chip, utilizes plasma enhanced chemical vapor deposition method to deposit layer of silicon dioxide in target base plate, and utilizes chemical mechanical milling method that silicon dioxide layer is polished to 2 microns.
Utilize Direct Bonding method, the silicon dioxide layer of target base plate and original substrate are carried out bonding to form bonding body; Bonding body is heated to 220 DEG C, and keeps 10 hours at such a temperature, bonding body is separated and makes film.
Film is carried out anneal at 300 ~ 600 DEG C, then carries out surface finish.
Film after polishing and Lithium Oxide 98min powder (solid) are put into encloses container heat, surrounding atmosphere is oxygen (O
2), temperature is 500 DEG C, and the time is 50 hours, takes out after film cooling, obtains lithium niobate monocrystal film after cleaning.
Now the very optical index of lithium niobate monocrystal film is lower than 2.202 (wavelength is 633 nanometers).In addition, the atomic ratio of lithium and niobium reaches more than 0.95:1, and this shows that the component of lithium niobate monocrystal film compares 1:1 close to ideal stoichiometric.
Embodiment 3
Original substrate is lithium niobate crystal chip, is 4 × 10 through overtreatment
16ions/cm
2helium ion (He
1+) inject, helium ion energy is 50keV.
Target base plate is lithium niobate crystal chip, depositing electrode in target base plate, then utilizes plasma enhanced chemical vapor deposition method to deposit layer of silicon dioxide in target base plate, and utilizes chemical mechanical milling method that silicon dioxide layer is polished to 2 microns.
Utilize Direct Bonding method, the silicon dioxide layer of target base plate and original substrate are carried out bonding to form bonding body; Bonding body is heated to 220 DEG C, and keeps 10 hours at such a temperature, bonding body is separated and makes film.
The film obtained and Lithium Oxide 98min powder (solid) are put into encloses container heat, surrounding atmosphere is oxygen (O
2), temperature is 500 DEG C, and the time is 50 hours, takes out after film cooling.
Finally, polishing is carried out to the surface of film, obtain electroded lithium niobate monocrystal film.
Now the very optical index of lithium niobate monocrystal film is lower than 2.202 (wavelength is 633 nanometers).In addition, the atomic ratio of lithium and niobium reaches more than 0.95:1, and this shows that the component of lithium niobate monocrystal film compares 1:1 close to ideal stoichiometric.
Embodiment 4
Original substrate is lithium niobate crystal chip, is 4 × 10 through overtreatment
16ions/cm
2helium ion (He
1+) inject, helium ion energy 230keV; Then, at the surface deposition layer of metal electrode injecting helium ion; Finally, utilize plasma enhanced chemical vapor deposition method to deposit layer of silicon dioxide on electrode layer, and utilize chemical mechanical polishing method that silicon dioxide layer is polished to target thickness.
Target base plate is lithium niobate crystal chip, utilizes Direct Bonding method that the silicon dioxide layer of target base plate and original substrate is carried out bonding to form bonding body; Bonding body is heated to 220 DEG C, and keeps 10 hours at such a temperature, bonding body is separated and makes film.
The film obtained and Lithium Oxide 98min powder (solid) are put into encloses container heat, surrounding atmosphere is oxygen (O
2), temperature is 500 DEG C, and the time is 50 hours, takes out after film cooling.
Finally, polishing is carried out to the surface of film, obtain the lithium niobate monocrystal film being with metal electrode.
Now the very optical index of lithium niobate monocrystal film is lower than 2.202 (wavelength is 633 nanometers).In addition, the atomic ratio of lithium and niobium reaches more than 0.95:1, and this shows that the component of lithium niobate monocrystal film compares 1:1 close to ideal stoichiometric.
Embodiment 5
Original substrate is lithium niobate crystal chip, is 4 × 10 through overtreatment
16ions/cm
2helium ion (He
1+) inject, helium ion energy 230keV.
Target base plate is lithium niobate crystal chip, utilizes plasma enhanced chemical vapor deposition method to deposit layer of silicon dioxide in target base plate, and utilizes chemical mechanical milling method that silicon dioxide layer is polished to 2 microns.
Utilize Direct Bonding method, the silicon dioxide layer of target base plate and original substrate are carried out bonding to form bonding body; Bonding body is heated to 220 DEG C, and keeps 10 hours at such a temperature, bonding body is separated and makes film.
Film is carried out anneal at 300 DEG C ~ 600 DEG C, then carries out surface finish.
Film after polishing and lithium nitrate are put into encloses container heat, temperature is 300 DEG C, and now lithium nitrate melts, and in molten state, thin film dipped in the lithium nitrate of molten state, setting-up time is 3 hours, and film takes out after arriving by setting-up time.
Finally, polishing is carried out to the surface of film, obtains lithium niobate monocrystal film.
Now the very optical index of lithium niobate monocrystal film is lower than 2.202 (wavelength is 633 nanometers).In addition, the atomic ratio of lithium and niobium reaches more than 0.95:1, and this shows that the component of lithium niobate monocrystal film compares 1:1 close to ideal stoichiometric.
Embodiment 6
Original substrate is lithium niobate crystal chip, is 4 × 10 through overtreatment
16ions/cm
2helium ion (He
1+) inject, helium ion energy is 230keV.
Target base plate is lithium niobate crystal chip, utilizes plasma enhanced chemical vapor deposition method to deposit layer of silicon dioxide in target base plate, and utilizes chemical mechanical milling method that silicon dioxide layer is polished to 2 microns.
Utilize Direct Bonding method, the silicon dioxide layer of target base plate and original substrate are carried out bonding to form bonding body; Bonding body is heated to 220 DEG C, and keeps 10 hours at such a temperature, bonding body is separated and makes film.
Film is carried out anneal at 300 ~ 600 DEG C, then carries out surface finish.
Film after polishing is placed in second container 20 as shown in Figure 2, Lithium Oxide 98min powder is placed into as in the first container 10 shown in Fig. 2, passes into oxygen (O from inlet mouth 11
2), oxygen flow is 1 liter/min, and the temperature of the first container 10 is set to 800 DEG C, and the temperature of second container 20 is set to 500 DEG C, and setting-up time is 20 hours, takes out after setting-up time reaches after film cooling, obtains lithium niobate monocrystal film after cleaning.
Now the very optical index of lithium niobate monocrystal film is lower than 2.202 (wavelength is 633 nanometers).In addition, the atomic ratio of lithium and niobium reaches more than 0.95:1, and this shows that the component of lithium niobate monocrystal film compares 1:1 close to ideal stoichiometric.
In sum, the method of manufacture monocrystal thin films of the present invention due to after transferring to target base plate at thin film layer in containing the environment of diffusant to film heating, lithium in monocrystal thin films is effectively compensated mutually, thus avoids the problem of monocrystal thin films disappearance lithium phase.
In addition, method of the present invention can produce nanometer grade thickness, uniform film thickness, component close to the monocrystal thin films of ideal stoichiometric ratio.
More than describe the preferred embodiment of the present invention in detail; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant and combination to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (10)
1. manufacture a method for the monocrystal thin films of near stoichiometric proportion, described method comprises the steps:
By ion implantation by the ion implantation surface to original substrate, thus in original substrate, form thin film layer, separating layer and remaining matter layer, wherein, thin film layer is positioned at the surface of original substrate, separating layer is between thin film layer and remaining matter layer, and the ion distribution of injection is in separating layer;
Make the thin film layer of target base plate and original substrate, and then utilize wafer bonding method original substrate and target base plate to be bonded together, to form bonding body;
Para-linkage body heats, and thin film layer is separated with remaining matter layer;
After thin film layer is separated with remaining matter layer, heat in the predetermined container that diffusant is housed with the temperature of 200 DEG C ~ 700 DEG C to thin film layer, wherein, diffusant comprises at least one in Lithium Oxide 98min and lithium nitrate.
2. method according to claim 1, wherein, diffusant is the mixture of Lithium Oxide 98min or Lithium Oxide 98min and Lithium niobium trioxide.
3. method according to claim 2, wherein, in the step heated thin film layer, passes into oxygen to predetermined container, makes thin film layer be heated to make Lithium Oxide 98min to be diffused in thin film layer at the temperature of 200 DEG C ~ 700 DEG C.
4. method according to claim 3, wherein, described predetermined container comprises: for placing the first container of diffusant, one end of the first container is provided with inlet mouth; For placing the second container of film, one end of second container is provided with air outlet; For the first container being connected to the pipeline of second container; To the primary heater that the first container heats; And to the secondary heater that second container heats.
5. method according to claim 1, wherein, diffusant is the mixture of at least one in lithium nitrate or SODIUMNITRATE, saltpetre and lithium nitrate.
6. method according to claim 5, wherein, in the step heated thin film layer, is immersed in thin film layer and is in the diffusant of molten state, makes thin film layer be heated to make lithium ion to be diffused in thin film layer at the temperature of 200 DEG C ~ 700 DEG C.
7. method according to claim 1, wherein, described method is also included in after para-linkage body carries out the step heated and before the step heated thin film layer, under the condition of 300 DEG C ~ 600 DEG C, carry out anneal to thin film layer.
8. want the method described in 1 according to right, wherein, described method is carried out surface finish process to thin film layer, and/or after the step heated thin film layer, is carried out surface finish process to thin film layer before being also included in the step to thin film layer heating.
9. method according to claim 1, wherein, target base plate is coated with silicon dioxide layer or is coated with electrode layer and silicon dioxide layer, and making the thin film layer of silicon dioxide layer and original substrate, to form bonding body; Or on the surface of the thin film layer of original substrate, be coated with electrode layer and silicon dioxide layer, and silicon dioxide layer is contacted with target base plate, to form bonding body.
10. method according to claim 1, wherein, carries out in the step heated at para-linkage body, under vacuum or be greater than 1 normal atmosphere and para-linkage body carries out heating thin film layer is separated with remaining matter layer under being less than 300 atmospheric atmosphere.
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| CN201410252850.0A CN104862784B (en) | 2014-06-09 | 2014-06-09 | A kind of method for the monocrystal thin films for manufacturing near stoichiometric proportion |
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| CN201410252850.0A CN104862784B (en) | 2014-06-09 | 2014-06-09 | A kind of method for the monocrystal thin films for manufacturing near stoichiometric proportion |
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| EP3525347A4 (en) * | 2016-10-06 | 2020-09-23 | Shin-Etsu Chemical Co., Ltd. | Composite substrate and method of manufacturing composite substrate |
| CN112382563A (en) * | 2020-11-13 | 2021-02-19 | 济南晶正电子科技有限公司 | Ion implantation thin film wafer separation method, single crystal thin film, and electronic component |
| CN112410885A (en) * | 2020-11-10 | 2021-02-26 | 珠海光库科技股份有限公司 | Lithium niobate single crystal film and manufacturing method thereof |
| CN115207206A (en) * | 2022-09-16 | 2022-10-18 | 济南晶正电子科技有限公司 | Near-stoichiometric composite film and preparation method thereof |
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