GB2123423A - Purification of trialkyl gallium - Google Patents
Purification of trialkyl gallium Download PDFInfo
- Publication number
- GB2123423A GB2123423A GB08317631A GB8317631A GB2123423A GB 2123423 A GB2123423 A GB 2123423A GB 08317631 A GB08317631 A GB 08317631A GB 8317631 A GB8317631 A GB 8317631A GB 2123423 A GB2123423 A GB 2123423A
- Authority
- GB
- United Kingdom
- Prior art keywords
- adduct
- ether
- gallium
- trialkyl
- gallium compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052733 gallium Inorganic materials 0.000 title description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title description 7
- 238000000746 purification Methods 0.000 title description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 62
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 35
- 150000002259 gallium compounds Chemical class 0.000 claims abstract description 27
- 238000009835 boiling Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 238000004508 fractional distillation Methods 0.000 claims abstract description 5
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 claims description 13
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 13
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- -1 trimethyl gallium Chemical class 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000927 vapour-phase epitaxy Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 229910000070 arsenic hydride Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910021478 group 5 element Inorganic materials 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- MCMSPRNYOJJPIZ-UHFFFAOYSA-N cadmium;mercury;tellurium Chemical compound [Cd]=[Te]=[Hg] MCMSPRNYOJJPIZ-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960005419 nitrogen Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method of preparing a trialkyl gallium compound (eg trimethyl gallium) in a relatively pure form comprises the steps of: (i) forming an adduct of the trialkyl gallium compound with an ether of the formula R1R2O, having a boiling point at least 50 Celsius degrees above the boiling point of the trialkyl gallium compound; (ii) removing volatile impurities by evacuation or distillation at a temperature below the adduct decomposition temperature; and (iii) heating the adduct at a temperature at which the adduct dissociates to form the trialkyl gallium compound as a vapour, and separating the trialkyl gallium compound by fractional distillation of its vapour.
Description
SPECIFICATION
The preparation of relatively pure metal alkyls
The present invention relates to the preparation of relatively pure metal alkyls useful in the preparation of compound semi-conductor materials.
Compound semiconductor materials, eg materials such as gallium arsenide, indium phosphide, gallium phosphide and cadmium mercury telluride, are well known materials having uses in the electronics industry in such applications as microwave oscillators, semiconductor light emitting diodes and lasers, and infrared detectors.
Such materials have been made in the past by forming, usually on a substrate crystal, one or more active layers, by the method of vapour phase epitaxy (VPE).
It has been known for some time to produce by VPE compound semiconductors of the form MAQA where MA is Group III element and QA iS Group V element by reacting a trialkyl of the element MA with a gaseous compound, eg a hydride, of the Group V element QA. This method is a suitable method of preparing gallium arsenide from Ga(CH3)3 and AsH3 for example.
More recently, another approach has been used in the preparation of Ill-V semiconductor compounds. Adducts of trialkyl compounds of both MA and QA, ie adducts of the form MA(RA)3 . QA(RB)3, where RA and RB are trialkyls have been formed, eg (CH3)3Ga .
P(C2Hs)3 and (CH2)3 Ga . N(C2H5)3. These adducts provide a favourable route to the required semiconductor materials because (i) they are less sensitive than the pure alkyls
MAQA to moisture and oxygen; (ii) they may be easily purified by sublimation or zone refining; and (iii) they may be decomposed pyrolytically at normal pressure to give the required semiconductor material either alone or in the presence of a group V hydride.
Since both of the methods outlined above involve the use of a trialkyl gallium compound in the case where the required semiconductor is a gallium compound trialkyl gallium compounds, particularly trimethyl gallium, have become important precursor materials in the manufacture of semiconductor materials.
It is well known to those skilled in the art that the presence of impurities in semiconductor materials has a profound effect on the electrical and other properties of the materials.
In order to control the properties it is therefore desirable to produce such materials in a high purity form. This means that the precursor materials such as trialkyl gallium compounds used in the manufacture of the semiconductor materials are desirably as pure as possible.
Known methods of preparing trialkyl gallium compounds involve the interaction of gallium halides with organic compounds of magnesium, zinc or aluminium or the interaction of metallic gallium with dialkyl compounds of mercury.
The trialkyl gallium compounds produced by all of these known methods contain traces of the starting materials as impurities and require further purification.
Methods of purifying trimethyl gallium by fractionating are known but have disadvantages.
For example the required column may need to be long and the first fraction of the product collected usually has to be discarded. The final product may have a purity level which could be improved.
According to the present invention in a first aspect a method of preparing a trialkyl gallium compound in a relatively pure form comprises the steps of: (i) forming an adduct of the trialkyl gallium compound with an ether of the formula R1R20, having a boiling point at least 50 Celsius degrees above the boiling point of the trialkyl gallium compound; (ii) removing volatile impurities by evacuation or distillation at a temperature below the adduct decomposition temperature; and (iii) heating the adduct at a temperature at which the adduct dissociates to form the trialkyl gallium compound as a vapour, and separating the trialkyl gallium compound by fractional distillation of its vapour.
Preferably the ether R,R20 is present in excess during the method.
Preferably, the trialkyl gallium compound is trimethyl gallium or triethyl gallium.
The organic radicals R1 and R2 may be aromatic or aliphatic radicals. They are preferably alkyl or phenyl radicals. Preferably R,R20 is an ether having a boiling point more than 1 00 C above that of the trialkyl gallium compound. Preferably the radicals R, and R2 each independently have from 1 to 9 carbon atoms, and together preferably have between 7 and 1 2 carbon atoms inclusive.
Desirably, R,R2O is di-isopentyl ether (3,3dimethylpropyl ether) but it may also be diphenyl ether or anisole (phenylmethyl ether).
Volatile impurities are preferably removed by evacuation at ambient temperature (- 20"C). Alternatively, or in addition, the adduct may be heated at a temperature of between 20"C and 1 20 C below the temperature required to decompose the adduct to remove volatile impurities. The adduct may be contained in a vessel which is heated by an oil bath, eg of paraffin wax, in which case the relevant temperature is that of the oil bath.
In the case where the trialkyl gallium compound is trymethyl gallium and the ether is diisopentyl ether the dissociation or decomposition is preferably carried out by heating the vessel containing the adduct in an oil bath, eg paraffin wax, at an oil bath temperature of between 180"C and 200"C, preferably 1 90 C. The dissociation is preferably preceded by heating at an oil bath temperature of between 80"C and 140"C which is sufficient to drive off impurities but insufficient to cause dissociation of the adduct.
The adduct may be formed by reacting together the ether and the trialkyl gallium in a less pure form than the final product, ie in a form to be purified.
Alternatively, the adduct may be made by other methods. For example Ga(CH3)3.dpe, where dpe is di-isopentyl ether, may be formed by reacting the alloy Mg5Ga2 with Mel and excess dpe, ie dpe in a concentration > 100 molar % of the molar % of Ga present.
In this case the overall preparative route to the pure trimethyl gallium is preferred to the known methods (mentioned above) for the production of trimethyl gallium containing trace impurities followed by purification of the product since the known methods of preparing the impure trimethyl gallium contain more stages and are hence more costly than this particular route.
Alternatively, the adduct may be formed by first producing the adduct (Alk)3Ga.RARBO where (Alk)3 is the required trialkyl group and
RARBO is a more volatile ether, such as diethyl ether, ie an ether whose boiling point is not 50"C or more higher than the boiling point of the compound (AIk)3Ga. The ether radical
RARBO may then be displaced in the adduct by R,R2O by radical exchange reaction preferably by the addition of excess R1R20 to the adduct (Alk)3Ga.RARBO.
Trimethyl gallium diethyl ether adduct may conveniently be converted into trimethyl gallium di-isopentyl ether adduct in this way.
Where (Alk)3Ga.RARBO is trimethyl gallium diethyl ether adduct (or other adduct containing an ether radical) this can conveniently be prepared by the electrolytic method described in a copending UK Patent Application No 8223418 (and the UK Application-to be filed---claiming priority from it) by the present
Applicant. A methylmagnesium halide (eg.
iodide) containing excess of the methyl halide in the ether is electrolysed using a sacrificial gallium pool anode (at about 70"C).
The adduct (CH3)3Ga.dpe may alternatively be produced directly by an analogous electrolytic procedure.
The intermediate adduct (Alk)3Ga. RARBO where produced may be prepared by other routes, eg by (i) reacting the alloy Mg5Ga2 with a methyl halide, eg Mel in excess ether
RARBO, or (ii) reacting the Grignard reagent
MeMgQ, where Q is a halogen eg Br, with gallium chloride in the ether RARBO.
In any event purification of trimethyl gallium by the method according to the first aspect of the present invention can be carried out more cheaply than prior art purification
methods because a shorter fractionating col
umn may be employed and all of the trimethyl gallium fraction collected may be useful thus
reducing the overall cost of the method.
This results from the fact that volatile im
purities are removed from the trimethyl gal
lium whilst it is combined with the ether in the form of a stable adduct.
The purity level of the product may also be
improved by using the method according to
the first aspect.
Although distillation of an adduct of a high
boiling ether and trimethyl gallium is known
in the prior art this has not been used as a
method of producing the pure gallium com
pound since it has not involved the step of the
removal of volatile impurities prior to the
distillation.
According to the present invention in a
second aspect there is provided a trialkyl
gallium compound in relatively pure form pro
duced by the method according to the first
aspect.
Examples of methods embodying the first
aspect of the invention will now be described.
Example 1
The homogeneous alloy Ga2Mg5 was first
obtained in a pure form by melting together
and mixing stoichiometric quantities of gal
lium and magnesium in a sealed, induction
heated graphite tube located in a sealed silica
tube.
Dry methyl iodide (62.5 ml, 1 mole) was
then added slowly, with stirring, to a suspen
sion of finely ground sample of the Ga2 Mg5 alloy (0.3 molar in Ga) in dry di-isopentyl
ether. The reaction was conducted in a nitro
gen atmosphere, and about 2 mg of iodine
was added to initiate the reaction. The reac
tion is exothermic and the rate of addition of
methyl iodide was such that the mixture- re
mained very hot without external heating.
During the course of the addition of methyl
iodide the initially dark mixture lightened con
siderably as magnesium iodide was deposited.
After all the methyl iodide had been added
the flask containing the mixture was heated
externally by a paraffin wax bath located on a
hot plate at a bath temperature of between 80"C and 90'C for about 2 hrs with stirring
until, upon complete reaction, the reaction
mixture became pure white. Most unreacted
methyl iodide was removed by adding fresh
magnesium powder and further heating the
mixture at 60 C for (Although this was not essential).
The mixture was then fractionally distilled
by heating at a bath temperature of about 100"C and distilling through a 22 cm long
X 1.5 cm diameter column packed with
Fenske helicles. The first fraction collected by
heating at this moderate temperature was a
small quantity of methyl iodide (boiling point 41-43"C). This fraction was readily sepa
rated. The distillation was continued at this
temperature until the vapour pressure of un reacted methyl iodide fell and no further methyl iodide distilled over.
Pure trimethyl gallium (boiling point 55-56 C) was then collected by heating the mixture at a bath temperature of about 1 90 C for about 6 hr. This temperature is above the decomposition temperature of the adduct formed.
Since the boiling point of the trimethyl gallium is much less than that of the diisopentyl ether (boiling point 1 60 C) the former was readily separated in the fractionating column and collected when the two dissociated from the adduct by heating at 1 90 C.
None of the trimethyl gallium fraction collected had to be discarded. All was useful material.
The trimethyl gallium product was checked by mass spectrometry and found to be relatively pure.
Example 2
Impure Me3Ga (0.1 7 moles) was added with stirring to a large excess of di-isopentyl ether (0.98 moles). When the exothermic reaction had subsided the mixture was stirred at room temperature for 1 2 hr. The Me3Ga.dpe adduct so formed was then fractionally distilled as in Example 1. (Me = methyl).
In another experiment not forming part of the present invention but carried out for purposes of comparison when trimethyl gallium contaminated with methyl iodide but in the absence of di-isopentyl ether in the form of an adduct was heated trimethyl gallium required only moderate external heating (90-100tC) for distillation. However, great difficulty was experienced in removing the methyl iodide.
This showed that the adduct formation (as in
Examples 1 and 2) is necessary in order to remove the methyl iodide. The methyl iodide may in fact be removed from the trimethyl gallium by carrying out the procedure of
Example 2.
The formation and then fractional distillation of a trimethyl gallium di-isopentyl ether adduct can also facilitate the removal of impurities other than methyl iodide. For example, impurities such as the volatile alkyls of Group
II and Group VI elements are removed in the fractional distillation process at much lower temperatures than the temperature (1 80 C) required for distillation of the trimethyl gallium.
Example 3
A solution of methyl magnesium iodide was first prepared by the dropwise addition of methyl iodide (22.7 g, 0.16 moles) to a stirred suspension of magnesium turnings (1.8 g, 0.075 moles) in diethyl ether (200 ml). The rate of addition of methyl iodide was such that the reaction mixture boiled under reflux without external heating. Addition of methyl iodide was stopped when all the magnesium had been consumed. The reaction mixture contained excess methyl iodide at this stage.
The diethyl ether solution of methylmagnesium iodide containing excess methyl iodide was then electrolysed in an atmosphere of dry oxygen free nitrogen using a Pt cathode (1 X 1 cm plate) and a sacrificial gallium pool anode (about 20-40 g). The mixture was heated to 70"C (using a wax bath) and was stirred continuously throughout the reaction.
An applied voltage of 100 volts gave a current of 30 mA which increased during the reaction. The reaction was allowed to proceed for 72 hours after which time the reaction mixture was allowed to cool. After filtration the diethyl ether was removed in vacuo. The pure liquid product was separated from residual methylmagnesium iodide by vacuum distillation (60 C) into a cold trap at about -196"C.
The product, whose structure was confirmed by 'H nuclear magnetic resonance spectroscopy (nmr), mass spectroscopy (ms) and infra-red absorption spectroscopy (ir), was trimethyl gallium diethyl ether adduct.
Di-isopentyl ether (20 cm3) was added in excess to the trimethyl gallium diethyl ether adduct at ambient temperature. A radical exchange reaction took place and the diethyl ether evolved was removed in vacuo at ambient temperature. Analysis showed that all of the diethyl ether had been displaced.
The resulting solution containing trimethyl gallium di-isopentyl ether adduct was subsequently converted into pure trimethyl gallium by heating at 190"C and collecting the trimethyl gallium in a fractionating column (boiling point 55-56"C) as in Example 1.
Example 4
To a suspension of Mg5Ga2 (59g) in anisole (600 cm3) was added methyl iodide (90 cm3) containing 12 (10 mg) over a period of 1 hour.
The solution became hot without boiling. The black solution containing unreacted alloy was refluxed for 24 hours (using a heating mantle) during which time a white precipitate formed.
Most of the unreacted methyl iodide (boiling point 42"C) was removed by distillation at an oil bath temperature of 100 C. More anisole (100 cm3) was added and the suspension heated to an oil bath temperature of 150 C.
Trimethyl gallium (boiling point 56"C) was distilled through a fractionating column and was collected. The yield was 36 g. Mass spectroscopic studies showed contamination by methyl iodide.
Crude trimethyl gallium produced by this method was then slowly added to anisole (250 cm3). Volatile impurities were removed by pumping (evacuation) at room temperature (20"C) and then again at an oil bath temperature of 60"C. The mixture was heated to an oil bath temperature of 150 C whereupon pure trimethyl gallium (boiling point 56 C) distilled through the fractionating column and was collected. The yield was 10 g. Mass spectroscopic studies confirmed purification of the trimethyl gallium.
Example 5
An analogous procedure to Example 4 was followed using diphenyl ether insted of the anisole. In this case the distillation temperature (of the oil bath) was 140"C. The yield of pure trimethyl gallium obtained from 22 g of crude material was 14 g.
Trimethyl gallium samples produced by the method of the above Examples have proved suitable for use in growing high quality epitaxial layers of GaAs (from the reaction of
Ga(CH3)3 and AsH3) with carrier concentrations of from 3 to 4.5 X 1015 Cm-3 at 298K which are better quality layers than those produced from commercially available trimethyl gallium.
Claims (6)
1. A method of preparing a trialkyl gallium compound in a relatively pure form which method comprises the steps of: (i) forming an adduct of the trialkyl gallium compound with an ether of the formula R,R2Q, having a boiling point at least 50 Celsius degrees above the boiling point of the trialkyl gallium compound; (ii) removing volatile impurities by evacuation or distillation at a temperature below the adduct decomposition temperature; and (iii) heating the adduct at a temperature at which the adduct dissociates to form the trialkyl gallium compound as a vapour, and separating the trialkyl gallium compound by fractional distillation of its vapour.
2. A method as claimed in claim 1 and wherein the ether R'R2Q is present in excess during the method.
3. A method as claimed in claim 1 or claim 2 and wherein the trialkyl gallium compound is triethyl gallium or trimethyl gallium.
4. A method as claimed in claim 1, 2 or 3 and wherein R, and R2 are independently selected from phenyl and alkyl radicals.
5. A method as claimed in claim 1, 2, 3 or 4 and wherein R1 and R2 each independently have from 1 to 9 carbon atoms and together have between 7 and 12 carbon atoms inclusive.
6. A method as claimed in any one of the preceding claims and wherein R,R20 is selected from di-isopentyl ether, diphenyl ether and anisole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08317631A GB2123423B (en) | 1982-06-29 | 1983-06-29 | Purification of trialkyl gallium |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8218820 | 1982-06-29 | ||
| GB838305165A GB8305165D0 (en) | 1983-02-24 | 1983-02-24 | Preparation of relatively pure metal alkyls |
| GB08317631A GB2123423B (en) | 1982-06-29 | 1983-06-29 | Purification of trialkyl gallium |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8317631D0 GB8317631D0 (en) | 1983-08-03 |
| GB2123423A true GB2123423A (en) | 1984-02-01 |
| GB2123423B GB2123423B (en) | 1985-11-27 |
Family
ID=27261643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08317631A Expired GB2123423B (en) | 1982-06-29 | 1983-06-29 | Purification of trialkyl gallium |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2123423B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0130005A2 (en) * | 1983-06-17 | 1985-01-02 | The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and | The preparation of metal alkyls |
| WO1985004405A1 (en) * | 1984-03-26 | 1985-10-10 | The Secretary Of State For Defence In Her Britanni | The preparation of metal alkyls |
| JPS62185090A (en) * | 1986-02-10 | 1987-08-13 | Sumitomo Chem Co Ltd | Purification of alkylgallium |
| EP0372138A1 (en) * | 1987-01-23 | 1990-06-13 | Morton International, Inc. | Process for preparing or purifying group III-A organometallic compounds |
| US5043462A (en) * | 1989-04-28 | 1991-08-27 | Messer Greisheim | Process for the production of gallium-alkyl compounds |
| WO1993010125A1 (en) * | 1991-11-19 | 1993-05-27 | Air Products And Chemicals, Inc. | Purification of tri-alkyl compounds of group 3a metals |
| WO1993010126A1 (en) * | 1991-11-19 | 1993-05-27 | Air Products And Chemicals, Inc. | Process for the preparation of trialkyl gallium compounds |
| WO1994001438A1 (en) * | 1992-07-02 | 1994-01-20 | Air Products And Chemicals, Inc. | Process for the preparation of trialkyl compounds of group 3a metals |
| US5455364A (en) * | 1993-12-14 | 1995-10-03 | Sumitomo Chemical Company, Ltd. | Process for removing an impurity in organometallic compound |
| WO2000037475A1 (en) * | 1998-12-19 | 2000-06-29 | Epichem Limited | Process and apparatus for production of organometallic compounds |
| US6482968B1 (en) | 1999-05-21 | 2002-11-19 | Akzo Nobel Nv | Purification of an organometallic compound |
| EP1705719A1 (en) * | 2005-03-23 | 2006-09-27 | Nichia Corporation | Methods for producing trialkyl gallium |
| CN102020669A (en) * | 2010-12-22 | 2011-04-20 | 江苏南大光电材料股份有限公司 | Method for industrially preparing trimethyl gallium |
| CN102020670A (en) * | 2010-12-22 | 2011-04-20 | 江苏南大光电材料股份有限公司 | Method for industrially preparing triethyl gallium |
-
1983
- 1983-06-29 GB GB08317631A patent/GB2123423B/en not_active Expired
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0130005A2 (en) * | 1983-06-17 | 1985-01-02 | The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and | The preparation of metal alkyls |
| EP0130005A3 (en) * | 1983-06-17 | 1985-10-02 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And | The preparation of metal alkyls |
| US4604473A (en) * | 1983-06-17 | 1986-08-05 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Preparation of metal alkyls |
| WO1985004405A1 (en) * | 1984-03-26 | 1985-10-10 | The Secretary Of State For Defence In Her Britanni | The preparation of metal alkyls |
| US4720561A (en) * | 1984-03-26 | 1988-01-19 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Preparation of metal alkyls |
| USRE33292E (en) * | 1984-03-26 | 1990-08-07 | The Secretary Of State For Defence In Her Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Preparation of metal alkyls |
| JPS62185090A (en) * | 1986-02-10 | 1987-08-13 | Sumitomo Chem Co Ltd | Purification of alkylgallium |
| EP0372138A1 (en) * | 1987-01-23 | 1990-06-13 | Morton International, Inc. | Process for preparing or purifying group III-A organometallic compounds |
| US5043462A (en) * | 1989-04-28 | 1991-08-27 | Messer Greisheim | Process for the production of gallium-alkyl compounds |
| WO1993010125A1 (en) * | 1991-11-19 | 1993-05-27 | Air Products And Chemicals, Inc. | Purification of tri-alkyl compounds of group 3a metals |
| WO1993010126A1 (en) * | 1991-11-19 | 1993-05-27 | Air Products And Chemicals, Inc. | Process for the preparation of trialkyl gallium compounds |
| US5248800A (en) * | 1991-11-19 | 1993-09-28 | Shell Research Limited | Process for the preparation of trialkyl gallium compounds |
| US5473090A (en) * | 1992-07-02 | 1995-12-05 | Air Products And Chemicals, Inc. | Process for the preparation of trialkyl compounds of group 3a metals |
| WO1994001438A1 (en) * | 1992-07-02 | 1994-01-20 | Air Products And Chemicals, Inc. | Process for the preparation of trialkyl compounds of group 3a metals |
| US5455364A (en) * | 1993-12-14 | 1995-10-03 | Sumitomo Chemical Company, Ltd. | Process for removing an impurity in organometallic compound |
| WO2000037475A1 (en) * | 1998-12-19 | 2000-06-29 | Epichem Limited | Process and apparatus for production of organometallic compounds |
| GB2358632A (en) * | 1998-12-19 | 2001-08-01 | Epichem Ltd | Process and apparatus for production of organometallic compounds |
| US6495707B1 (en) | 1998-12-19 | 2002-12-17 | Epichem Limited | Process and apparatus for production of organometallic compounds |
| GB2358632B (en) * | 1998-12-19 | 2004-01-28 | Epichem Ltd | Process and apparatus for the continuous production of organometallic compounds |
| DE19983803B3 (en) * | 1998-12-19 | 2017-05-04 | Sigma-Aldrich Co. | Method and use of a device for producing trimethylgallium |
| US6482968B1 (en) | 1999-05-21 | 2002-11-19 | Akzo Nobel Nv | Purification of an organometallic compound |
| EP1755175A1 (en) * | 2005-03-23 | 2007-02-21 | Nichia Corporation | Methods for producing trialkyl gallium |
| EP1903618A1 (en) | 2005-03-23 | 2008-03-26 | Nichia Corporation | Method for producing trialkyl gallium |
| US7667063B2 (en) | 2005-03-23 | 2010-02-23 | Nichia Corporation | Method for producing trialkyl gallium |
| US8278470B2 (en) | 2005-03-23 | 2012-10-02 | Nichia Corporation | Method for producing trialkyl gallium |
| EP1705719A1 (en) * | 2005-03-23 | 2006-09-27 | Nichia Corporation | Methods for producing trialkyl gallium |
| CN102020669A (en) * | 2010-12-22 | 2011-04-20 | 江苏南大光电材料股份有限公司 | Method for industrially preparing trimethyl gallium |
| CN102020670A (en) * | 2010-12-22 | 2011-04-20 | 江苏南大光电材料股份有限公司 | Method for industrially preparing triethyl gallium |
| CN102020669B (en) * | 2010-12-22 | 2013-01-09 | 江苏南大光电材料股份有限公司 | Method for industrially preparing trimethyl gallium |
| CN102020670B (en) * | 2010-12-22 | 2013-01-09 | 江苏南大光电材料股份有限公司 | Method for industrially preparing triethyl gallium |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8317631D0 (en) | 1983-08-03 |
| GB2123423B (en) | 1985-11-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |