CN105609585B - A kind of gas source molecular beam epitaxy material growth method of component alternation transition zone - Google Patents
A kind of gas source molecular beam epitaxy material growth method of component alternation transition zone Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 230000007704 transition Effects 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000000171 gas-source molecular beam epitaxy Methods 0.000 title claims abstract description 18
- 230000002146 bilateral effect Effects 0.000 claims abstract description 3
- 229910000070 arsenic hydride Inorganic materials 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 6
- 230000035772 mutation Effects 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 229910052785 arsenic Inorganic materials 0.000 description 11
- 239000000758 substrate Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910000673 Indium arsenide Inorganic materials 0.000 description 5
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011982 device technology Methods 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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Abstract
The present invention relates to a kind of gas source molecular beam epitaxy material growth method of component alternation transition zone, including：Component alternation transition zone containing two kinds or more V group elements in hetero-junctions side or bilateral material is grown using gas source molecular beam epitaxy growing method, grown with two or more gaseous sources, III electron gun is solid-state, and line is switched by shutter realizes control；V pencil of families source is gaseous state, by pressure or Flow-rate adjustment V pencil of families intensity of flow or V III ratios, obtains component alternation transition zone.The transition zone obtained with the material growth method of the present invention can effectively alleviate the negative effect that can be brought with spike or lattice and component mutation to device performance in heterojunction device at heterogeneous interface, so as to be advantageous to improve device performance or Development of Novel device.
Description
Technical field
The invention belongs to semiconductor photoelectronic device preparation field, more particularly to a kind of gaseous source of component alternation transition zone
Mbe Grown growing method.
Background technology
In recent years, with SQW, the isostructural research of superlattices, energy band engineering is in semiconductor devices and opto-electronic device
Important function has been played in field, and the application of energy band engineering relies on the perfect of heteroj unction technologies.Due to prohibiting with different materials
The hetero-junctions of bandwidth enable to device have different from homogeneity junction device function, thus heterojunction phototransistor,
Have in the design of the device such as hetero junction laser diode and avalanche photodide (Avalanche Photodiode, APD) important
Application.But because the lattice constant of heterojunction boundary two layers of material is different, easily cause interface deformation, formed dislocation and
Defect；In addition, two kinds of different size of energy gaps of material, easily produce band rank at heterojunction boundary, producing can band spike
Effect, had an impact to carrier transporting in hetero-junctions.But, the development of growth technique technology, it is heterojunction semiconductor
The satisfactory growth of material provides condition, if molecular beam epitaxy technique is in the growth of control atomic layer yardstick and dynamics Controlling growth
Superiority in terms of mechanism, the basis of development is provided for the various opto-electronic devices with labyrinth design.
For example, APD is because with multiplier effect and than PN detector with higher sensitivity and detectivity, especially suitable for
The detection of faint optical signal, obtain increasing attention and application.Since occurring last century the seventies APD, APD
Structure experienced an evolution updated.The APD structures of early stage still use PIN structural, work in higher anti-
To under voltage, device noise is higher.In order to reduce device noise, researcher devises the knot of separate absorbent area and gain region
Structure, increase a multiplication region with relatively broad forbidden band outside uptake zone and form uptake zone and multiplication region separation (Separated
Absorption and Multiplication, SAM) structure, the introducing of broad stopband multiplication region can reduce device dark current
With noise, and uptake zone and multiplication plot structure can with relatively independent optimize.But the band rank that the mutation of energy band is brought,
The transition time of carrier is added, causes the reduction of response device speed, then people are also in narrow band gap uptake zone and broadband
Transition zone is introduced between gap multiplication region and can be formed uptake zone and multiplication region separation with spike effect, there is transition zone with reducing
(Separated Absorption Grading and Multiplication, SAGM) structure, reduce further device
Noise, improve the response speed of device.Again by introducing charged region, form so-called uptake zone charged region and multiplication region separation,
With transition zone (Separated Absorption Grading Charge and Multiplication, SAGCM) structure,
With modulated electric fields and carrier ionization process can be modulated.
Therefore, merely from Material growth angle, the APD extension numbers of plies are more, to accurate control layers of material component, limitation
Extension interface layer counterdiffusion has high requirements, while every layer of doping concentration need to be controlled accurately, particularly the realization of low concentration,
Phase counterdiffusion between charge layers and other layers, and heterojunction boundary is required and can be precisely controlled.Given birth to as material in recent years
The leading technology in long field, molecular beam epitaxy can not only grow complete heterojunction boundary, and component to hetero-junctions, mix
Miscellaneous, each thickness degree can accurately control in the range of atom magnitude.At present, for pertaining only to single V races source of the gas element material
For the APD of system, by the optimization to doping, device architecture, energy band and electric field etc., APD research has been achieved for
Remarkable progress.But, for the growth of As, P mixed system material, more problem, the hole such as using InP as multiplication region are still suffered from
The InGaAsP APD of multiplication type；InGaAsP APD even using InAlAs the electron multiplication type of multiplication region, have not yet to see so far
All reports.Its main cause is probably by caused by Material growth difficulty, it is contemplated that both are that uptake zone and multiplication region separate
Structure, and be respectively the material system containing arsenic (As) and phosphorus (P), because multiplication region structural material is compared to uptake zone structural material
For, it is desirable to energy gap is bigger, and this needs the transition zone (Grading) for introducing phosphorus containing arsenic and component alternation to rise in device design
Acted on to alternation, stop of the band offsets to carrier can be reduced with spike effect to reduce, so as to improve APD response speed
Degree.
However, due to only 40 DEG C of white phosphorus burning-point, cavity pollution is easily caused, solid-state phosphorus source brings very big inconvenience to use.And
Gas source molecular beam epitaxy (GSMBE) technology is while solid-state Source Molecule Beam Epitaxy Technique feature is kept, in phosphorus source controlling party
There is the advantages of notable in face, and it is with AsH3And PH3For group V source, depended on pressure control V races ratio, it is prepares high-quality InP-base and phosphorous
Iii-v fine structure material provides advantage with device.It is also development respectively as uptake zone and the arsenic of multiplication region
(As) and the APD devices of the SAGCM structures of phosphorus (P) material system provide possibility.Even so, enter using GSMBE technologies
During row Material growth, As, P switching times should be typically reduced, this aspect is due to that both switchings are more slow, between the time
Every longer, handoff procedure easily produces dislocation and with rank in interface location；On the other hand, AsH3And PH3For hypertoxic gas, tail gas needs
Processing with caution, the part that pump falls will also result in waste.Therefore, the growth for As, P mixed system material is needed in growth technique
More consideration is made in control and parameter designing etc..
The content of the invention
The technical problems to be solved by the invention are to provide a kind of gas source molecular beam epitaxy material of component alternation transition zone
Expect growing method, the transition zone obtained with this method can effectively alleviate the energy band spike at heterogeneous interface in heterojunction device
Or the negative effect that lattice and component mutation are brought to device performance, so as to be advantageous to improve device performance or Development of Novel device
Part.
A kind of gas source molecular beam epitaxy material growth method of component alternation transition zone of the present invention, including：
Grown using gas source molecular beam epitaxy growing method in hetero-junctions side or bilateral material and contain two kinds or more V
The component alternation transition zone of race's element, is grown with two or more gaseous sources, and III electron gun is solid-state, and line is by shutter
Control is realized in switching；V pencil of families source is gaseous state, by pressure or Flow-rate adjustment V pencil of families intensity of flow or V-III ratios, obtains component alternation
Transition zone.
The component alternation transition zone is in strain regime.
The thickness of the component alternation transition zone is ten nanometer scales.
The III electron gun is In and Ga.
The V pencil of families source is AsH3And PH3。
Beneficial effect
(1) energy band is gradual change in the transition layer structure obtained with the material growth method of the present invention, can effectively be reduced
It can be influenceed caused by band mutation with spike effect, while the gradual change of energy gap also corresponds to an equivalent electric field be present,
The force direction that acts on electronics and hole can be made on the contrary, can not only thus reduce the barrier effect with rank to carrier transport,
And can reduce the transition time of carrier, be advantageous to that device performance is greatly improved.
(2) component is gradual change in the transition layer structure obtained with the material growth method of the present invention, suitable for hetero-junctions
Interface both sides, have different lattice constants two kinds of materials lattice transition, so as to reduce because lattice period is abnormal on interface
Become, the dislocation and defect of formation.
(3) the transition layer structure thought grown for other using source of the gas, comprising can band mutation or component and lattice lose
The growth for the material system matched somebody with somebody equally has reference, has good versatility；It can be used for effectively alleviating hetero-junctions
The negative effect that can be brought with spike or lattice and component mutation to device performance in device at heterogeneous interface, so as to be advantageous to
Improve device performance or Development of Novel device.
Brief description of the drawings
Fig. 1 is the obtained heterojunction boundary transition layer structure schematic diagram of the present invention, wherein represent element species A, B, C and
More than D style formulas mark, to distinguish over the form of subseript for representing component；
Fig. 2 is containing (In0.53Ga0.47As)0.55-x(InP)0.45+xComponent (energy band) alternation transition zone
(In0.53Ga0.47As)0.55(InP)0.45Avalanche photodide material structure schematic diagram.
Fig. 3 is containing (In0.83Ga0.17As)1-x(InP)xThe In of component (energy band) alternation transition zone0.83Ga0.17As infrared electros
Material for detector structural representation.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
The growth of the InGaAsP avalanche photodiode structure materials of 1.25 microns of cutoff wavelength in InP substrate
(1) need to grow (In0.53Ga0.47As)0.55(InP)0.45Avalanche photodide epitaxial material, using uptake zone
Charged region and multiplication region separation, there is transition zone (SAGCM) structure, schematic diagram is as shown in Fig. 2 i.e.：InP materials are as cushion
And carried out highly doped (while being used as lower contact layer, n by the use of Si>2×1018cm-3), (In0.53Ga0.47As)0.55(InP)0.45Material is made
Low-doped Si or (n~1 × 10 that undope are carried out for absorbed layer16cm-3), undope (In0.53Ga0.47As)0.55-x(InP)0.45+x
Component graded bed as the transition zone among absorbed layer and charge layer, more low-doped Si InP as charge layer (n~2 ×
1017cm-3), the low-doped or InP materials that undope are as dynode layer, highly doped Be InP Window layers (p~3 × 1018cm-3)
With highly doped Be In0.53Ga0.47As contact layers (p>2×1018cm-3)；
(2) gas source molecular beam epitaxy method is used, the lining of detector is used as using semi-insulating or conductive InP monocrystal materials
Bottom, preparation growth is first passed through before formal growth and determines to grow InP, In of Lattice Matching in InP substrate0.53Ga0.47As and
(In0.53Ga0.47As)0.55(InP)0.45When the growth conditions such as electron gun furnace temperature, underlayer temperature and V races pressure value, with growth
InP、(In0.53Ga0.47As)0.55(InP)0.45And In0.53Ga0.47As underlayer temperature is respectively 490 DEG C, 510 DEG C and 530 DEG C
Example discusses the growing method of material；
(3) first with 490 DEG C of growth thickness of underlayer temperature after oxide desorption processing is carried out to Epi-Ready InP substrates
About 0.2 μm of highly doped Si n-type InP cushions, n>2×1018cm-3；
(4) and then with the low-doped of about 1.5 μm of 510 DEG C of growth thickness of underlayer temperature or the n-type to undope
(In0.53Ga0.47As)0.55(InP)0.45Absorbed layer, n are about 1 × 1016cm-3；
(5) the characteristics of source of the gas boosting of V races is rapid, decompression is slow, the interface mistake for growing As, P mixed system are considered
Layer is crossed, PH is carried out respectively using five steps3Rise fixed pressure value and AsH3The fixed pressure value of drop, AsH3During decompression, pump 0.5s is often walked.Simultaneously
Substrate is cooled with 0.02 DEG C/s speed, and III In and Ga sources are risen respectively with 0.09 DEG C/s and 0.3 DEG C/s speed,
Cooling, during which keep group III source shutter to open all the time, 20s is arranged to per the one-step growth time, after five steps, Ga source temperatures drop
Extremely it is less than (In0.53Ga0.47As)0.55(InP)0.45Shutter is closed after 30 DEG C required of temperature, obtains gross thickness about 30nm component
(energy band) alternation transition layer structure；
(6) and then with 490 DEG C of InP charge layers for growing the more low-doped Si of 70nm of underlayer temperature, n is about 2 × 1017cm-3；
(7) next using 490 DEG C of growth thickness of underlayer temperature as 0.8 μm undope or low-doped Si InP dynode layers,
N is about 1 × 1016cm-3；
(8) InP Window layers using 490 DEG C of growth thickness of underlayer temperature as 0.45 μm of highly doped Be are continued, p is about 3 ×
1018cm-3；
(9) it is last again by PH3Switch to AsH3Atmosphere, and after underlayer temperature is risen into 530 DEG C, about 0.15 μm of growth thickness,
Highly doped Be In0.53Ga0.47The upper contact layers of As, p>2×1018cm-3；
(10) terminate growth, cool under protective atmosphere, take out epitaxial material and carry out necessary test and device technology system
Make.
Embodiment 2
The growth of the InGaAs panel detector structure materials of 2.6 microns of cutoff wavelength in InP substrate
(1) need grow room temperature 50% by wavelength be 2.6 μm of In0.83Ga0.17As p-i-n type infrared photoelectric detectors
Structure epitaxial material, schematic diagram determine to grow in InP substrate as shown in figure 3, first passing through preparation growth before formal growth
Electron gun furnace temperature, underlayer temperature and V races pressure value during the InAsP cushions of the InP of Lattice Matching and different As and P components etc.
Growth conditions.
(2) gas source molecular beam epitaxy method is used, the lining of detector is used as using semi-insulating or conductive InP monocrystal materials
Bottom, first with about 0.2 μm of 490 DEG C of growth thickness of underlayer temperature after oxide desorption processing is carried out to Epi-Ready InP substrates
Highly doped Si n-type InP cushions, n~3 × 1018cm-3；
(3) the doped n-type InAsP gradient buffers for and then with 510 DEG C of growth As, P components of underlayer temperature increasing respectively, subtracting
Layer, electron concentration is 3 × 1018cm-3, it is followed successively by：The InAs that 0.3 μm of thickness0.1P0.9Layer, the InAs that 0.3 μm of thickness0.2P0.8
Layer, the InAs that 0.3 μm of thickness0.3P0.7Layer, the InAs that 0.3 μm of thickness0.4P0.6Layer, the InAs that 0.3 μm of thickness0.5P0.5Layer, thickness
0.3 μm of InAs0.61P0.39Layer, the gradient-structure strain as virtual substrate structure for discharging；
(4) then using about 1.5 μm of 510 DEG C of growth thickness of underlayer temperature, In components as 83% low-doped n-type
In0.83Ga0.17For As materials as absorbed layer, n is about 3 × 1016cm-3；
(5) it is the interface transition layer of growth As, P mixed system, PH is carried out respectively using 4 steps3Rise fixed pressure value and AsH3Drop
Fixed pressure value, AsH3During decompression, pump 0.5s is often walked.And III In and Ga sources are distinguished with 0.04 DEG C/s and 0.3 DEG C/s speed
Heating-cooling, during which keep group III source shutter to open all the time, 25s is arranged to per the one-step growth time, after four steps, Ga source temperatures
It is brought down below growth In0.83Ga0.17Shutter, PH are closed after 30 DEG C of temperature needed for As3And AsH3Pressure value is then growth Window layer
InAs0.61P0.39The condition of layer, and obtain gross thickness about 30nm component (energy band) alternation transition layer structure；
(6) it is last again with 510 DEG C of underlayer temperature, about 0.6 μm of growth thickness, highly doped Be InAs0.61P0.39Window layer and
Upper contact layer, p>5×1018cm-3；
(7) terminate growth, cool under protective atmosphere, take out epitaxial material and carry out necessary test and device technology system
Make.
Claims (5)
1. a kind of gas source molecular beam epitaxy material growth method of component alternation transition zone, including：
Grown using gas source molecular beam epitaxy growing method in hetero-junctions side or bilateral material containing two kinds or more V races members
The component alternation transition zone of element, is grown, III electron gun is solid-state, and line is switched by shutter with two or more gaseous sources
Realize control；V pencil of families source is gaseous state, by pressure or Flow-rate adjustment V pencil of families intensity of flow or V-III ratios, obtains component alternation transition
Layer.
2. a kind of gas source molecular beam epitaxy material growth method of component alternation transition zone according to claim 1, its
It is characterised by：The component alternation transition zone is in strain regime.
3. a kind of gas source molecular beam epitaxy material growth method of component alternation transition zone according to claim 1, its
It is characterised by：The thickness of the component alternation transition zone is ten nanometer scales.
4. a kind of gas source molecular beam epitaxy material growth method of component alternation transition zone according to claim 1, its
It is characterised by：The III electron gun is In and Ga.
5. a kind of gas source molecular beam epitaxy material growth method of component alternation transition zone according to claim 1, its
It is characterised by：The V pencil of families source is AsH3And PH3。
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