CN105002471A - Method for preparing KTiOPO4 single crystal thin film through ion implantation in combination with chemical etching - Google Patents
Method for preparing KTiOPO4 single crystal thin film through ion implantation in combination with chemical etching Download PDFInfo
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- CN105002471A CN105002471A CN201510308632.9A CN201510308632A CN105002471A CN 105002471 A CN105002471 A CN 105002471A CN 201510308632 A CN201510308632 A CN 201510308632A CN 105002471 A CN105002471 A CN 105002471A
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Abstract
The invention relates to a method for preparing a KTiOPO4 single crystal thin film through ion implantation in combination with chemical etching. According to the method, H or He ions are injected into a crystal sample within the low-energy range (100-60,000 keV), the injected ion dosage ranges from 1*1,016 ions/square centimeter to 10*1,016 ions/square centimeter, and the injection temperature is a room temperature or a low temperature; then, annealing treatment is conducted on the sample, the annealing temperature ranges from 200 DEG C to 600 DEG C, the total duration of annealing ranges from 10 seconds to 2 hours; etching is conducted on the sample through a chemical reagent, and crystal thin film stripping is achieved. By the adoption of the method, after He ions with the energy of 2,000 keV and the dosage of 4*1,016 are injected into the Z-tangential KTP sample, the annealed sample is put into an HF solution to be etched, and thin film stripping is achieved. By the adoption of the method, the KOTiPO4 crystal thin film with the thickness of 5 micrometers is obtained, and the way of obtaining the KTP single crystal thin film by conducting ion injection in combination with chemical etching is utilized for the first time so far.
Description
Technical field
The present invention relates to one utilizes ion implantation technique to prepare optical crystal (KTiOPO in conjunction with chemical etching
4) method of film, belong to optical crystal material technical field.
Background technology
Optics just progressively substitutes electronic devices and components and is applied in information and signals process, because, electronic devices and components of comparing, opto-electronic device has a lot of advantages, as bandwidth is comparatively large, wavelength-division multiplex, the advantages such as reduce power consumption.Have the optical crystal material of excellent photoelectricity, piezoelectricity, ferroelectric and non-linear character, as LiNbO
3, LiTaO
3and KTiOPO
4have a wide range of applications Deng in surface wave filter, optical waveguides, electrooptic modulator, frequency multiplication conversion, information storage etc.Along with the integrated and microminiaturization development trend of opto-electronic device and product, more opto-electronic device is integrated in chip the hot topic research becoming current.Integrated optics is just by the light path of difference in functionality, and optical component gathers together, and achieves the integrated of optical information processing system and microminiaturization.The integrated needs of electronic devices and components prepares monocrystalline silicon thin film, such as (Silicon On Insulate, SOI).Therefore, realize that the height of optics is integrated must prepare optical crystal material film.A variety of method is had to make membrane structure at present, as chemical Vapor deposition process, radio frequency sputtering method, molecular beam epitaxy, and pulsed laser deposition, but these methods are all difficult to produce high-quality monocrystal material.In addition, as epitaxial growth method is restricted to lattice match, this just has strict demand to substrate material.Domestic patent (CN201410199630.6) discloses and a kind ofly utilizes the ion implantation method preparing potassium titanium oxide phosphate film, low-energy light ion H ion or He ion are injected in potassium titanium oxide phosphate material at normal temperatures, material after injecting light ion is bundled on substrate by Resin adhesive, maybe will inject the material Direct Bonding after light ion on substrate, injection face is bonded on substrate; Anneal is carried out to above-mentioned sample.But it adopts the method for directly binding to peel off epitaxial, to the smooth of material surface and smoothness requirements higher; And the condition realizing peeling off due to binding is harsher, have certain restriction to injection ion dose, energy and annealing conditions, the implantation dosage being such as applicable to bind has a strict use range, i.e. " window " of so-called dosage.Meanwhile, the energy of injection can not be too high, otherwise the strain of injecting generation is not enough to too thick film is stripped down.But up to now, also do not realize the relevant report of the method for optical crystal film preparation in conjunction with chemical etching by ion implantation technique.
Summary of the invention
The object of the invention is to adopt ion implantation and chemical etching to combine, realize peeling off the method that lower one deck scope is the optional optical crystal material film preparation of thickness in 400 nanometers to 20 micron.That mentions can produce by the method for ion implanted junction conjunction chemical etching the film possessing high quality single crystal characteristic.The ultimate principle of this method is: by high dosage (1 × 10
16~ 10
17ion/square centimeter) light ion (as H
+or He
+) be injected in sample, again by sample through a series of annealing process, finally put into chemical solution and soak etching processing, sample can at ion implantation end-of-range, namely damage maximum position place to realize optionally etching, thus peel off the intact material film of next layer lattice structure.
For achieving the above object, the present invention takes following technical scheme:
One utilizes ion implanted junction conjunction chemical etching to prepare KTiOPO
4the method of monocrystal thin films, comprises step as follows:
(1) optical crystal sample is provided;
(2) carry out ion implantation to optical crystal sample, form crystalline damage layer, wherein injecting ion energy range is 100keV ~ 6000keV, and the implantation dosage of ion is greater than 1 × 10
16ion/square centimeter;
(3) the sample surfaces coated with resins after injection protected or bind with substrate, then carrying out anneal;
(4) sample after anneal is carried out polished finish;
(5) the sample chemical agent after polished finish is carried out selective etch, separate crystal film.
Preferably, the implantation dosage scope of ion is 1 × 10
16ion/square centimeter ~ 1 × 10
17ion/square centimeter.Efficiency is etched preferably to ensure.Because etch rate and selectivity are all closely related with implant damage, implantation dosage is lower than 1 × 10
16during ion/square centimeter, lens lesion degree is lower, and etching efficiency can reduce.
Preferably, the ion of injection is H ion and He ion.
Preferably, describedly ion implantationly to carry out under normal temperature or cold condition.
Preferably, benzocyclobutene is adopted to carry out coating protection to sample surfaces.
Preferably, the step that the sample after described injection and substrate are bound is sample after injecting and substrate directly carries out thermocompression bonding or be that bonding medium carries out thermocompression bonding with benzocyclobutene.
Preferably, described anneal is short annealing or the annealing that heats up gradually.
Preferably, the temperature of described anneal is: 200 DEG C ~ 600 DEG C.10 seconds ~ 2 hours total time of annealing.
Preferably, described polished finish is mechanical rough grinding or chemically machinery polished.
Preferably, described chemical agent comprises any in hydrofluoric acid and/or nitric acid, potassium hydroxide and/or saltpetre.
Preferably, described etching temperature scope is 20 DEG C-450 DEG C, if select hydrofluoric acid or nitric acid to etch, etching temperature is lower, is usually no more than 60 degree.And adopt potassium hydroxide and/or nitrate to etch, need alkali or nitrate to be in molten state, both fusing points are within 450 DEG C.
In step (2), light ion is H ion and He ion.The injection face of sample is polished surface.Implantation temperature is under normal temperature or cold condition.Select the energy size injecting ion to determine the thickness of the film finally stripped down, energy is larger, and film thickness is larger.Implantation dosage is larger, and the lattice damage of initiation is larger, and the speed that film etching is peeled off also can correspondingly be accelerated.
Mentioning sample surfaces coating material in step (3) is benzocyclobutene, binding sample method two kinds used is: one, with photoresist spinner at sample injection face or substrate material surface spin coating benzocyclobutene (BCB) monomer or resin, the thickness of coating is by the parameter of photoresist spinner, as initial acceleration, rotating speed, whirl coating time, and the decision such as the concentration of benzocyclobutene.Then the sample scribbling benzocyclobutene is heated to 100 DEG C to 350 DEG C scopes, makes sample surfaces form protective layer, or injection face and substrate are pressed together, realize binding.Two, the method for Direct Bonding is adopted, first the planeness of sample and substrate surface will be got well, chemical reagent is adopted to clean and use deionized water rinsing to sample and substrate surface, final sample and the clean nitrogen of substrate surface dry up, and namely the slight pressure that applies that surface both is stacked together realize the two bonding.
The annealing time mentioned in step (3) is determined by annealing temperature and annealing way.Annealing way is divided into heat up gradually annealing and short annealing.Heating up to be annealed into gradually is elevated to temperature required by sample from room temperature gradually, remains on the temperature corresponding time of arrival.Short annealing is that required temperature realizes in advance, is directly placed on by sample in required temperature environment and keeps the corresponding time.But the short annealing mode of short period can reach the effect identical with the annealing of lesser temps long period under the annealing way that heats up gradually at a higher temperature.The time of the higher needs of annealing temperature is shorter, and the temperature that short annealing needs is high, but annealing time can correspondingly reduce.
The finishing method mentioned in step (4), one is mechanical rough grinding method, by silicon carbide or boron carbide powder water-soluble and be applied to mill, sample is fixed on hand-ground on fixture.Two is chemistry and mechanical coupling fashion polishing processes, sample is put in polisher lapper, and is coated with diamond grinding and polishing cream respectively at mill and carries out polishing.Clean mill afterwards, then the polishing fluid dripped containing silica suspension is cooked further meticulous polishing.
In etching liquid temperature described in step (5), temperature depends on selected etching reagent, such as, is room temperature by acid solution hydrofluoric acid and (or) nitric acid temperature.Also can heated solution a little, like this can corresponding raising etch rate.Concentration about hydrofluoric acid in solution and (or) nitric acid can require to do corresponding dilution according to the selectivity of etching, and concentration range is 1% to 70%.According to potassium hydroxide and (or) saltpetre etching, the temperature of needs is then relatively higher.
The above-mentioned method steps preparing optical crystal material film has exemplary illustration in FIG.
Light ion is injected into KTiOPO according to above-mentioned steps by us
4in crystal prototype, then carry out surface-coated protection or binding, anneal, last etching processing realizes film and peels off.Wherein, by helium ion (He
+) be injected into and achieve film after in sample and peel off.Be 2000keV by energy, dosage is 4 × 10
16the helium ion of ion/square centimeter injects along sample Z crystal orientation, by by slow heating mode anneal, and thin film under then etching 2 hours in HF solution and peeling off.The end face microscope photograph of the potassium titanium oxide phosphate film having us to strip down in fig. 2, the thickness showing film in figure is 5 microns, consistent with the ion implantation range that our simulation and experiment is measured.
Beneficial effect of the present invention:
1. the chemical etching method that this patent adopts only needs effects on surface to do coating protection, does not have other requirements to material surface.Energy and the dosage scope of application of injecting ion in the present invention are wide, are easy to peel off after injection.
2. the present invention is the selective etching principle caused based on implant damage, and namely damage zone etch rate is obviously faster than the district that is without damage.The affected layer of lattice can be produced after ion implantation ktp crystal, the lattice of damage is easy to be eroded by chemical acidic solution, the speed of the corrosion in affected layer can be do not damage lattice hundreds of to up to ten thousand times, this have optionally etch character, the epitaxial etching any thickness is made to become possibility, therefore be no matter the film preparation of 400 nanometers or 20 micron thickness, in method and technique be on all four.
3. compared with the method for existing acquisition material film, advantage of the present invention and positively effect are: utilize ion implantation and method that is chemical etching can obtain the good monocrystal material of crystalline network; And this method is easy to realize.
Accompanying drawing explanation
Fig. 1 is method steps brief description figure used in the present invention;
Fig. 2 is KTiOPO in the embodiment of the present invention
4end face shape figure after etching.
Wherein, Fig. 1 (a) peels off under using benzocyclobutene bonding pattern; Peel off under Fig. 1 (b) Direct Bonding mode.Fig. 2 (a) scanning electron microscopic observation sample end face etching situation (b) scanning electron microscopic observation sur-face peeling situation
Embodiment
Further illustrate below in conjunction with embodiment.
Embodiment 1
By potassium titanium oxide phosphate material (size: 10mm × 10mm × 1mm) clean, be injected in the tangential potassium titanium oxide phosphate material of Z under adopting the He ion normal temperature of energy 2000keV, implantation dosage 4 × 10
16ion/square centimeter; Carry out anneal after injection, annealing temperature is progressively raised to 350 degrees Celsius by room temperature, keeps 30 minutes at 350 degrees Celsius, and finally in the HF solution of mass concentration 5%, at 20 DEG C, etching realizes film stripping for 2 hours.
Embodiment 2
By potassium titanium oxide phosphate material (size: 10mm × 10mm × 1mm) clean, be injected in the tangential potassium titanium oxide phosphate material of Z under adopting the He ion normal temperature of energy 150keV, implantation dosage 8 × 10
16ion/square centimeter; Carry out anneal after injection, annealing temperature is progressively raised to 350 degrees Celsius by room temperature, keeps 30 minutes at 350 degrees Celsius, and finally in the salpeter solution of mass concentration 5%, at 60 DEG C, etching realizes film stripping for 2 hours.
Embodiment 3
By potassium titanium oxide phosphate material (size: 10mm × 10mm × 1mm) clean, be injected in the tangential potassium titanium oxide phosphate material of Z under adopting the He ion normal temperature of energy 6000keV, implantation dosage 1 × 10
17ion/square centimeter; Carry out anneal after injection, annealing temperature is progressively raised to 400 degrees Celsius by room temperature, keeps 30 minutes at 400 degrees Celsius, finally in the molten state potassium hydroxide solution of mass concentration 5%, within 2 hours, realizes film in 360 DEG C of etchings and peels off.
Embodiment 4
By potassium titanium oxide phosphate material (size: 10mm × 10mm × 1mm) clean, be injected in the tangential potassium titanium oxide phosphate material of Z under adopting the He ion normal temperature of energy 2000keV, implantation dosage 4 × 10
16ion/square centimeter; Carry out anneal after injection, annealing temperature is progressively raised to 600 degrees Celsius by room temperature, keeps 10 seconds at 600 degrees Celsius, finally in the potassium nitrate solution of molten state, within 2 hours, realizes film in 360 DEG C of etchings and peels off.
Embodiment 5
By potassium titanium oxide phosphate material (size: 10mm × 10mm × 1mm) clean, be injected in the tangential potassium titanium oxide phosphate material of Z under adopting the He ion normal temperature of energy 500keV, implantation dosage 4 × 10
16ion/square centimeter; Carry out anneal after injection, annealing temperature is progressively raised to 200 degrees Celsius by room temperature, keeps 2 hours at 200 degrees Celsius, and finally in the saltpetre of molten state and the mixing solutions of potassium hydroxide, at 450 DEG C, etching realizes film stripping for 2 hours.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. one kind utilizes ion implanted junction conjunction chemical etching to prepare KTiOPO
4the method of monocrystal thin films, is characterized in that, comprises step as follows:
(1) optical crystal sample is provided;
(2) carry out ion implantation to optical crystal sample, form crystalline damage layer, wherein injecting ion energy range is 100keV ~ 6000keV, and the implantation dosage of ion is greater than 1 × 10
16ion/square centimeter;
(3) the sample surfaces coating benzocyclobutane olefine resin after injection protected or bound with substrate, then carrying out anneal;
(4) sample after anneal is carried out polished finish;
(5) the sample chemical agent after polished finish is carried out selective etch, separate crystal film.
2. the method for claim 1, is characterized in that, the implantation dosage scope of ion is 1 × 10
16ion/square centimeter ~ 10 × 10
16ion/square centimeter.
3. the method for claim 1, is characterized in that, the ion of injection is H ion or He ion.
4. the method for claim 1, is characterized in that, describedly ion implantationly to carry out under normal temperature or cold condition.
5. the method for claim 1, is characterized in that, the step that the sample after described injection and substrate are bound is sample after injecting and substrate directly carries out bonding or be that bonding medium carries out thermocompression bonding with benzocyclobutene.
6. the method for claim 1, is characterized in that, described anneal is short annealing or the annealing that heats up gradually.
7. the method for claim 1, is characterized in that, the temperature of described anneal is: 200 DEG C ~ 600 DEG C, 10 seconds ~ 2 hours total time of annealing.
8. the method for claim 1, is characterized in that, described polished finish is mechanical rough grinding or chemically machinery polished.
9. the method for claim 1, is characterized in that, described chemical agent comprises any in hydrofluoric acid and/or nitric acid, potassium hydroxide and/or saltpetre.
10. the method for claim 1, is characterized in that, described etching temperature scope is 20 DEG C-450 DEG C.
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| CN108448095A (en) * | 2018-03-23 | 2018-08-24 | 南开大学 | A kind of sodium ion battery electrode material KTiOPO4Synthesis and application |
| CN111725298A (en) * | 2020-06-16 | 2020-09-29 | 深圳技术大学 | Rutile titanium dioxide single crystal film-substrate material heterostructure and preparation method thereof |
| 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 |
| CN113381286A (en) * | 2021-06-02 | 2021-09-10 | 山东大学 | Method for preparing crystal film by ion beam reinforced corrosion |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108448095A (en) * | 2018-03-23 | 2018-08-24 | 南开大学 | A kind of sodium ion battery electrode material KTiOPO4Synthesis and application |
| CN108448095B (en) * | 2018-03-23 | 2021-04-09 | 南开大学 | Sodium ion battery electrode material KTiOPO4Synthesis and application of |
| CN111725298A (en) * | 2020-06-16 | 2020-09-29 | 深圳技术大学 | Rutile titanium dioxide single crystal film-substrate material heterostructure and preparation method thereof |
| CN111725298B (en) * | 2020-06-16 | 2022-02-18 | 深圳技术大学 | Rutile titanium dioxide single crystal film-substrate material heterostructure and preparation method thereof |
| 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 |
| CN113381286A (en) * | 2021-06-02 | 2021-09-10 | 山东大学 | Method for preparing crystal film by ion beam reinforced corrosion |
| CN113381286B (en) * | 2021-06-02 | 2023-03-03 | 山东大学 | Method for preparing crystal film by ion beam reinforced corrosion |
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