CN108183062A - A kind of method realized GaAsN epitaxial film silicon and efficiently adulterated - Google Patents

A kind of method realized GaAsN epitaxial film silicon and efficiently adulterated Download PDF

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CN108183062A
CN108183062A CN201711226329.XA CN201711226329A CN108183062A CN 108183062 A CN108183062 A CN 108183062A CN 201711226329 A CN201711226329 A CN 201711226329A CN 108183062 A CN108183062 A CN 108183062A
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gaasn
silicon
adulterated
epitaxial
incorporated
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赵雲
韩修训
董琛
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02395—Arsenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02584—Delta-doping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

The invention discloses a kind of method realized GaAsN epitaxial film silicon and efficiently adulterated, traditional (100) GaAs substrates are changed into the GaAsN materials that (n11) B GaAs substrates adulterate come epitaxially grown silicon using epitaxial growth means.The present invention utilizes (n11) B polar surfaces (i.e. As faces) that can form V, three key of high density (i.e. N or As), and construct the activated adoption position of N with reference to the high electronegativity characteristic of N, the generation of silicon atom and N complexs can effectively be inhibited, so as to effectively improve the amount of being incorporated to of silicon in GaAsN, the GaAsN films of silicon-controlled doping can be obtained.

Description

A kind of method realized GaAsN epitaxial film silicon and efficiently adulterated
Technical field
The present invention relates to the sides that a kind of orientation by changing substrate and polarity realization GaAsN epitaxial film silicon are efficiently adulterated Method belongs to ternary semiconductor thin-film material growing technology field.
Background technology
Realize controllable N-shaped doping and p-type doping for building the high-performance p-n junction sun in same semi-conducting material Energy battery is very important.Silicon（Si）It is widely applied N-shaped doped chemical in III-V race's semi-conducting material.But it is so far Only, the experiment and theoretical research that most of related Si are adulterated all concentrate on traditional GaAs material systems, for GaAsN material bodies Doping characteristic research in system is less, since there are the GaAsN materials that the mutual passivation of doped chemical Si and N lead to Si doping Electrical activity significantly weaken, thus doping of the Si in GaAsN materials again there are it is new the problem of.The experiment of early stage and theory are ground Study carefully result and have shown that SiGa-NAsTo presence, foreign atom Si can be changed into the localized modes center of deep energy level by shallow donor. And the method for first principle, which calculates, to be found：Compared to SiGa-NAsTo formation, in GaAsN formed (Si-N)AsDeep energy level Lower formation energy is only needed by main gap complex.Therefore, it is necessary to deeper into experimental study clarify doped chemical Si and N Mutual passivation mechanisms.On the other hand, a large amount of researchs in relation to improving GaAsN epitaxial layer qualities all concentrate on tradition (100) GaAs Substrate, and we have found that by the transformation to epitaxial surface atomic configuration is capable of the merging behavior of effective modulation doping atom.And Previously there are many researchs to report, turning for doping type can be realized in GaAs materials by changing the orientation of growth and surface polarity Become.But in GaAsN material systems, the research adulterated come Effective Regulation by changing the orientation of growth and surface polarity there is not yet Report.Therefore, finding a kind of controllable doped effective ways of high quality GaAsN epitaxial films not only has scientific value, but also With more realistic meaning.
Invention content
The purpose of the present invention is to provide a kind of methods realized GaAsN epitaxial film silicon and efficiently adulterated.
The key of the present invention is that solving mutual passivation of the GaAsN materials there are doped chemical Si and N in growth course makees With caused Si doping efficiencies it is relatively low the problem of.Due to the difference on atomic size and electronegativity, N atomic ratio doped chemical Si with The complex that N is formed more preferentially occupies As, three key of (n11) B aufwuchsplates.Therefore for GaAsN B polar surfaces, (n11) B Polar surface can effectively reduce the influence being incorporated to the doped chemical Si amounts of being incorporated to of N.The present invention, which proposes, utilizes epitaxial growth hand Traditional [100] epitaxial orientation is changed into [n11] orientation by section, and three key of high density is formed using (n11) B polar surfaces (i.e. As faces) V (i.e. N or As), and the activated adoption position of N is constructed with reference to the high electronegativity characteristic of N, it can effectively inhibit doped chemical The generation of Si and N complexs is so as to effectively improve the amount of being incorporated to of Si in GaAsN.
It is described to improve having for Si dopants in GaAsN by the way that traditional [100] epitaxial orientation is changed into [n11] orientation The effect amount of being incorporated to refers to traditional (100) GaAs substrates are changed into (n11) B GaAs substrates, epitaxial growth during extension Si adulterates GaAsN materials, is as follows：
A) the GaAs materials that (n11) B is orientated are selected as substrate, due to (n11) B polar surfaces (i.e. As faces) can be formed it is highly dense V, three key (i.e. N or As) is spent, due to the difference on atomic size and electronegativity, what N atomic ratio doped chemical Si and N was formed Complex more preferentially occupies V, three key of (n11) B aufwuchsplates.Therefore, V, three key be more advantageous to N effectively be incorporated to so as to Being incorporated to for the complex that Si and N formed is inhibited, and different with the selection of " n ", the density of V, three key in epitaxial surface It can be different；The density of three V, keys is higher, is more conducive to being incorporated to for Si dopants；
B) the GaAsN materials adulterated using epitaxial growth means come epitaxial growth Si.
The numerical value of the n is ordinarily selected to 2,3 or 5, that is, selects (211) B, (311) B or (511) B orientation GaAs materials are as substrate, and the density of three key active sites is declining successively in corresponding epitaxial surface.
The epitaxial growth means are sunk for chemical beam epitaxy (CBE), molecular beam epitaxy (MBE) or Metallo-Organic Chemical Vapor Product (MOCVD).
The mechanism of the present invention：It is illustrated by taking (311) B epitaxial orientations as an example.(n11) crystal face is considered as by (100) Face and (111) face are composed, and for (311) face, the contribution of corresponding two orientations crystal face is 1:1.According to Ga-As bond orientations Difference, containing [111] Ga orientation (311) crystal face be known as (311) A faces, containing [111] As orientation (311) crystal face be then known as (311) B Face.Two kinds of opposed polarity aufwuchsplates all there are three key mappings, three key mapping can regard as by two atoms on the ingredient of (100) face and (111) adatom on the ingredient of face is formed.For (311) A aufwuchsplates, there are a large amount of three keys for the polar surface III（Ga）Being incorporated to for doped chemical Si and N can be limited simultaneously, this can increase Si and N interaction probabilities in turn.It is this It is to occupy As in the form of Si and N form complex to a certain degree that interaction with N, which can cause Si to be entrained in,.It is and right (311) for B faces, which is then V (As or N).Due to the difference on atomic size and electronegativity, N atomic ratios Si The complex formed with N more preferentially occupies V, three key of (n11) B aufwuchsplates.For traditional (100) GaAs substrates, Adsorption position is all double bond position for III race and group Ⅴ element.Therefore, compared with traditional (100) epitaxial orientation, (311) B aufwuchsplates are rich in V, three key, in the case of identical Si doped sources and N sources are supplied during extension, will effectively inhibit Si and N The probability of complex is formed, so as to be effectively increased the amount of being incorporated to of Si in GaAsN.
Description of the drawings
Fig. 1 be GaAs (100), (111), the atomic structure schematic diagram of (211) and (311) crystal face.
Fig. 2 is the pass that the Si atomic concentrations measured in embodiment by Secondary Ion Mass Spectrometry (SIMS) change with N atomic concentrations It is curve.
Fig. 3 is free carrier concentration in the Si doping GaAsN materials of different orientation in embodiment 3 with the variation of N content Curve.Filled circles are to represent electronics, and open circles represent hole.It is worth noting that, to different orientation of growth GaAsN, N components Across range be inconsistent.
Specific embodiment
Using the GaAsN materials of chemical beam epitaxy (CBE) method growth Si doping, concrete technology and step are as follows：
Embodiment 1
As shown in Figure 1, ideal (n11) substrate crystal face can be regarded as being composed of (100) face and (111) face, right (311) with for (211) face, the contribution of both above face ingredient is 1 respectively in face:1 and 1:2.According to Ga-As bond orientations not Together, (n11) crystal face of the orientation containing [111] Ga is known as (n11) A faces, and (n11) crystal face of the orientation containing [111] As is then known as (n11) B Face.
Embodiment uses the epitaxial growth on (100), (211) B GaAs substrates respectively of chemical beam epitaxy (CBE) method The GaAsN epitaxial layers of about 1 μ m-thick.During extension, using triethyl-gallium (TEGa), three (dimethylamino) arsenic (TDMAAs) With monomethyl hydrazine (MMHy) respectively as Ga sources, As sources and N sources, the flow of TEGa and TDMAAs are controlled respectively 0.1,1.0 sccm.Silane (the SiH of 0.7sccm is fixed on by being passed through flow4) gas realizes the doping of Si in GaAsN materials, and The flow control of MMHy is 0,4,6,9 and 11 sccm, and what the flow for changing N sources was primarily used to research N is incorporated to what Si was adulterated It influences.The growth temperature of material is 460 DEG C.During the experiment, the doping efficiency of Si is determined using Secondary Ion Mass Spectrometry, and The carrier concentration for determining epitaxial film is tested with reference to Hall effect.
Embodiment 2
Using the GaAsN materials of molecular beam epitaxy (MBE) method growth Si doping, concrete technology and step are as follows：
(1) the GaAs materials that (n11) B is orientated is selected to illustrate by taking (311) A/B GaAs substrates as an example as substrate.
(2) (311) A/B GaAs N-shaped conductive substrates are put into molecular beam epitaxy (MBE) growth room's epitaxial growth Si doping GaAsN materials.During extension, during extension, using triethyl-gallium (TEGa), three (dimethylamino) arsenic (TDMAAs) and monomethyl hydrazine (MMHy) is respectively as Ga sources, As sources and N sources, and the flow of TEGa and TDMAAs control respectively 0.1,1.0 sccm.Silane (SiH4) gas that 0.7sccm is fixed on by being passed through flow realizes mixing for Si in GaAsN materials Miscellaneous, and the flow control of MMHy is 0,4,6,9 and 11 sccm, the flow for changing N sources is primarily used to being incorporated to Si of research N The influence of doping.The growth temperature of material is 460 DEG C.During the experiment, the doping of Si is determined using Secondary Ion Mass Spectrometry Efficiency, and Hall effect test is combined for determining the carrier concentration of epitaxial film.
By the success of above-mentioned growth technique Si doping is obtained in (100), (211) B and (311) A/B GaAs Growns In order to determine the doping situation of Si in GaAsN epitaxial films, SIMS analysis has been carried out to sample for N-shaped GaAsN materials （Fig. 2）And Hall effect test（Fig. 3）.From Fig. 3, we can see first, and extension obtains under all substrate orientations Si doping GaAs shows N-shaped conduction type, this shows in no N and fashionable, and III are that Si atoms preferentially occupy position. (311) carrier concentration of the lower GaAsN of A orientations is minimum in various orientations, the reason is that, a large amount of on (311) A aufwuchsplates Three III, keys are to be more advantageous to being incorporated to for Ga atoms, which directly results in Si and occupy probability reduction on III positions.This Analysis is also what is be consistent with the test result of SIMS below（Fig. 2）：The lower Si of (311) A orientations is real in the GaAs samples of different orientation The atomic concentration of border incorporation is minimum.
After N is incorporated to, the carrier concentration of different orientation sample shows notable difference with the variation relation of N content.Although With the increase of N content, the carrier concentration of different orientation GaAsN is all reducing, but reduces degree and be very different. (311) carrier concentration of A samples is reduced rapidly in the range of very narrow N content, it means that Si atoms and N atoms exist compared with Strong interaction.And find corresponding evidence in the result that this stronger Si-N interactions can also be tested in SIMS： Although (311) carrier concentration that A is orientated in GaAsN is being continuously reduced, as shown in Fig. 2, (1) being incorporated to N, Si's Atom content but has a little increase；(2) when further increasing the amount of being incorporated to of N, the atom content of Si maintains essentially in certain water In flat range.The interaction of Si-N reduces doping efficiencies of the Si as alms giver in namely (311) A GaAsN.
Above-mentioned experimental phenomena can be understood by following analysis：(311) a large amount of III, three key is simultaneously on A aufwuchsplates Being incorporated to for Si and N is limited, this but increases Si-N interaction probabilities in turn.It is this to lead to Si's with N interaction Doping is that As are occupied in the form of Si-N complexs to a certain extent, and the atomic concentration here it is Si has just started simultaneously in N Fashionable the reason of having increased slightly.With further increasing for the N amounts of being incorporated to, the interaction of Si-N can cause the Si of incorporation further Inactivation, (311) A Si-GaAsN are finally changed into p-type electric-conducting type.This means that the Si overwhelming majority of incorporation is because of Si-N It acts on and inactivates.
However for the GaAsN with B polar surfaces, when N components are less than 0.01, carrier concentration varies less （Fig. 3）.This may be interpreted as, and due to the difference on atomic size and electronegativity, N atomic ratio Si-N complexs more preferentially occupy (n11) V, three key of B aufwuchsplates.So in (211) B and (311) B samples, being incorporated to for N does not cause Si atomic concentrations Dramatically increase.On the contrary, N sources flow be more than 4 sccm after, have B polar surface epitaxial layers Si atomic concentrations but subtract rapidly Small, there are significantly different with (100) and (311) A samples for this phenomenon.The reason is that the N amounts of being incorporated to continue to increase, into one Step promotes the generation of Si-N complexs on aufwuchsplate.On the one hand, which can not be effective in the competition process with N It is incorporated on As positions；On the other hand, it is excessively compound inevitably to reduce the probability that Si occupies Ga as donor element.Therefore, exist (311) B of the higher N amounts of being incorporated to decays comparatively fast with carrier concentration in (211) B samples, and the practical incorporation of Si reduces.So And, it should be noted that do not change, and in B in (311) B of the high N amounts of being incorporated to and the conduction type of (211) B samples Si is orientated and A polarity aufwuchsplate as the efficiency of donor doping significantly better than (100) on polar growth face.

Claims (3)

  1. A kind of 1. method realized GaAsN epitaxial film silicon and efficiently adulterated, it is characterised in that will be traditional using epitaxial growth means (100) GaAs substrates change into (n11) B GaAs substrates come epitaxially grown silicon doping GaAsN materials.
  2. 2. the method as described in claim 1, it is characterised in that the epitaxial growth means are chemical beam epitaxy, molecular beam epitaxy Or metal organic chemical vapor deposition.
  3. 3. the method as described in claim 1, it is characterised in that the n is 2,3 or 5.
CN201711226329.XA 2017-11-29 2017-11-29 A kind of method realized GaAsN epitaxial film silicon and efficiently adulterated Pending CN108183062A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105405757A (en) * 2015-12-18 2016-03-16 中国科学院兰州化学物理研究所 Method for improving merging quantity of N in GaAsN epitaxial thin film and reducing generation of interstitial defect
CN105428225A (en) * 2014-09-10 2016-03-23 长春理工大学 Method of controlling doping concentration of N-type GaAs film by optimizing category of As molecule

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105428225A (en) * 2014-09-10 2016-03-23 长春理工大学 Method of controlling doping concentration of N-type GaAs film by optimizing category of As molecule
CN105405757A (en) * 2015-12-18 2016-03-16 中国科学院兰州化学物理研究所 Method for improving merging quantity of N in GaAsN epitaxial thin film and reducing generation of interstitial defect

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIUXU HAN ET AL: ""Growth orientation dependence of Si doping in GaAsN"", 《JOURNAL OF APPLIED PHYSICS》 *

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Application publication date: 20180619