Inorganic compounds

Abstract

The present invention relates to a manufacturing method for producing HGeCl3 from a homogeneous gas phase reaction between GeCl4 and H2 according to the following equation: JPEG2025540419000007.jpg9170

Description

[Technical Field]

[0001] Germanium-based electronic components ("germanium sti- bium telluride" or germanium antimony telluride, Ge x Sb y Te x+1.5y For the deposition of germanium (GST), germanium precursors that release Ge(II) during the deposition process are sought. Because these compounds are used in vapor-phase deposition, the germanium precursor must be highly volatile. One germanium compound that appears particularly attractive is HGeCl3 (germane trichloride or germanochloroform, CAS number: 1184-65-2). It has a boiling point of 75°C and is liquid at room temperature. Furthermore, it has a high germanium content (approximately 40 m%), ensuring a high germanium concentration in the gas phase. This is necessary to enable high deposition rates.

[0002] The academic literature describes the following reaction: 1) Wet Chemicals i) Reduction reaction of GeCl4 with phosphite in aqueous solution ii) Reduction of silane with GeCl4 in organic solvents 2) Heterogeneous gas phase reaction (HGR): i) Reaction of elemental germanium with dry HCl Ge+3HCl->HGeCl3+H2 (ideal reaction equation) ii) Reaction of GeCl2 with dry HCl gas GeCl2+HCl->HGeCl3 iii) Reaction of GeS with dry HCl gas GeS+3HCl->HGeCl3+H2S

[0003] Wet Chemicals: Although wet chemical syntheses are known, they are used to generate HGeCl3 in situ and in solution, and no one has reported the isolation of unstable HGeCl3 from solution. Medicinal Chemistry, 2009, 5, 382–384, describes the in situ synthesis of HGeCl3 in aqueous media starting from HGeCl4 or GeO2 with HCl / NaH2PO2, but does not describe isolation. The resulting HGeCl3 is then further reacted as is. Also, wet-chemically produced HGeCl3 is not used in the semiconductor industry, but is typically used in wet chemistry, (metal)organic chemistry, and pharmaceuticals. CA Ros-kamp et al., in "Encyclopedia of Reagents for Organic Syntheses," describes the synthesis of HGeCl3 starting from GeCl4 and tetramethyldisiloxane. However, the product is not isolated, but the formed HGeCl3 is further reacted at the reaction temperature to obtain the dioxane complex GeCl2 (dioxane).

[0004] As a result, this type of reaction was deemed inappropriate for the intended purpose described above and was not investigated further.

[0005] Regarding heterogeneous gas-phase reactions, reaction 2.i was first described in 1886. C. Winkler, J. prakt. Chem. 1886, 34, 177-229, showed the synthesis of HGeCl3 starting from Ge + HCl at red heat.

[0006] The "Handbook of Preparative Inorganic Chemistry" by Georg Brauer states on page 721 that it is possible to synthesize HGeCl3 starting from Ge + HCl.

[0007] Also, in the Journal of Physical Chemistry, 1926, 30, 1049-1054, L.M. Dennis describes the synthesis of HGeCl3 starting from Ge+HCl.

[0008] Various literature sources exist, according to which neat HGeCl can be obtained from this mixture by derivatization and workup of the intermediate isolated derivative. The final step requires distillation under reduced pressure, which entails a yield loss (81% based on the derivative). The procedure involves dissolving the crude mixture in diethyl ether, separating the formed two-phase system, and cracking the intermediate germane trichloride diethyl ether complex with aluminum trichloride.

[0009] In LM Dennis' Journal of Physical Chemistry, 1926, 30, 1049-1054 and in Georg Brauer's "Handbook of Preparative Inorganic Chemistry" on page 721, Reaction 2.ii is reported as an alternative to Reaction 2.i, making use of the equilibrium shown below. The problem here is that the GeCl2 used is temperature sensitive and tends to decompose above room temperature to form the so-called germanium subchloride. [ka] Since (x<2), the gradual decomposition ultimately leaves only germanium and germanium tetrachloride.

[0010] On page 721 of the "Handbook of Preparative Inorganic Chemistry" by Georg Brauer it is stated that it is possible to synthesize HGeCl3 starting from GeCl2 + HCl.

[0011] Also, LM Dennis, Journal of Physical Chemistry, 1926, 30, 1049-1054, describes the synthesis of HGeCl3 starting from GeCl2 + HCl, and notes that both the synthesis of GeCl2 and the subsequent reaction with HCl occur at temperatures above room temperature, with the result that the GeCl2 used is always contaminated with subchlorides, which is a major disadvantage.

[0012] Reaction 2.iii is described as an alternative to Reaction 2.ii in Georg Brauer's "Handbook of Preparative Inorganic Chemistry" (p. 721) and C.W. Moulton et al., JACS 1956, 78, 2702-2704. A yield of approximately 40% based on GeS is obtained, and it is described as the simplest (stable reactant GeS) and cleanest synthetic route, free of GeCl4 by-products. However, the H2S generated in the synthesis could cause problems because sulfur is chemically similar to tellurium in GST. As a result, we believe that sulfur in GST should not be present in the final product HGeCl3, since it could be expected to impair the functionality of the electronic components.

[0013] As mentioned above, compounds that release Ge(II) are particularly in demand, and HGeCl3, formally a Ge(IV) compound, can meet this demand since it already decomposes at room temperature (and decomposes more rapidly at higher temperatures and reduced pressures) according to the following equation: [ka] This advantage in application is simultaneously a disadvantage in larger-scale synthesis: HGeCl3 is a liquid, HCl is a gas, and GeCl2 is a solid (in each case at room temperature and pressure), so HCl slowly evolves into a gas while GeCl2 remains as a solid.

[0014] The challenge is to obtain a product from a stable process that is of the consistent quality and high purity required for use in the semiconductor device industry.

[0015] This problem is solved by a method for producing HGeCl3 from a homogeneous gas-phase reaction between GeCl4 and H2 according to the following equation: [ka] In various experiments, it was shown that careful reduction, i.e., approximating equimolar amounts of hydrogen in the reduction reaction of GeCl4 with hydrogen, can selectively lead to the desired product HGeCl3.

[0016] Surprisingly and completely unexpectedly, it has been found that in the reaction system Ge / GeCl4 / HGeCl3 / H2 / HCl all components are in equilibrium with one another and this reaction provides a solution to the problem of the present invention.

[0017] Furthermore, because the proportion of starting material GeCl4 is so small, this previously undescribed synthetic method yields HGeCl3 with very high purity (with respect to GeCl4 as a minor component) containing 80% of the desired trichlorogermane (HGeCl3), which is significantly higher than other methods described in the literature. The product obtained directly from the process can be used for applications in the semiconductor device industry without further purification.

[0018] Generally, the above methods using heterogeneous gas phase synthesis are not well suited or difficult to carry out in a continuous process due to the use of solid starting materials.

[0019] An advantage of the present invention is that both GeCl4 (a volatile liquid) and hydrogen (a gas) can be easily introduced into the reaction, thus facilitating a continuous process.

[0020] The inventors have found that the gas phase reaction proceeds in a furnace, preferably a tube furnace, with a hydrogen flux through the furnace of 0.5 L.min-1 .cm -2 Less than or equal to 0.4 L / min, preferably 0.4 L / min -1 .cm -2 Less than or equal to 0.3 L / min, preferably 0.3 L / min -1 .cm -2 It has been found that gas phase reactions give particularly desirable products when the flux is less than 0.1 L.min -1 .cm -2 It is preferable that it is higher than

[0021] It has further been found that when the gas phase reaction proceeds in a furnace, preferably a tube furnace, hydrogen (H2) and germanium tetrachloride (GeCl4) are fed to said furnace in a molar ratio of hydrogen (H2) to germanium tetrachloride (GeCl4) of 1:1 to 30:1, preferably 2:1 to 25:1.

[0022] It has also been found that the reaction product containing trichlorogermane obtained from the gas phase reaction is condensed preferably at a temperature lower than -80°C, more preferably at a temperature of -80°C to -200°C.

[0023] In general, the reaction of germanium tetrachloride (GeCl) with hydrogen (H) to obtain the desired product trichlorogermane (HGeCl) has been found to be a very robust reaction that can be carried out at temperatures between 600°C and 1200°C, more specifically between 800°C and 1200°C.

[0024] Suitable pressures can be applied over a wide range, generally reaction pressures of 100 mbar to 10,000 mbar, more particularly reaction pressures of 800 mbar to 2000 mbar, and especially pressures of about 1000 mbar have been found to be suitable.

[0025] Generally, the method includes the steps of generating a gas mixture of germanium tetrachloride (GeCl4) and a carrier gas.

[0026] This can be accomplished, for example, by exposing germanium tetrachloride (GeCl4) to temperature and pressure conditions sufficient to produce germanium tetrachloride (GeCl4) gas, and passing a stream of carrier gas through the germanium tetrachloride (GeCl4) gas, thereby producing a carrier gas stream containing germanium tetrachloride gas.

[0027] In another embodiment, a carrier gas stream is passed through liquid germanium tetrachloride (GeCl4) exposed to conditions sufficient to allow the generation of a carrier gas stream containing germanium tetrachloride (GeCl4) gas. In this embodiment, it may be advantageous to heat the germanium tetrachloride (GeCl4) to a temperature below its boiling point at ambient pressure. In particular, the germanium tetrachloride (GeCl4) is heated to a temperature between 30°C and 100°C, preferably between 40°C and 100°C, more preferably between 50°C and 100°C, and particularly between 50°C and 80°C at ambient pressure.

[0028] Other means for producing a carrier gas stream containing gaseous germanium tetrachloride may also be useful.

[0029] The carrier gas may be an inert gas or hydrogen, and more particularly, the carrier gas is selected from nitrogen, hydrogen, helium, neon, argon, hydrogen chloride, xenon, or a combination thereof.

[0030] If the carrier gas containing germanium tetrachloride (GeCl4) is different from hydrogen, hydrogen must be added as a reactant, which can be achieved by mixing with hydrogen.

[0031] In another embodiment, the carrier gas is hydrogen, thereby eliminating the need to add hydrogen to the carrier gas stream containing the gaseous germanium tetrachloride.

[0032] The carrier gas stream containing gaseous germanium tetrachloride is then preferably heated to a temperature of 600°C or higher, in particular to a temperature of 600°C to 1200°C or 800°C to 1000°C, more particularly to about 1000°C.

[0033] This can be achieved, for example, by passing a carrier gas stream containing gaseous germanium tetrachloride through a heat exchanger. In a simple version of this embodiment, a carrier gas stream containing gaseous germanium tetrachloride is passed through tubes located within a tube furnace.

[0034] The ratio of hydrogen (H2):germanium tetrachloride (GeCl4) is from about 1:1 to about 30:1, more specifically from about 2:1 to about 22:1.

[0035] Generally, a tube furnace setup comprising, for example, a quartz glass tube having an internal diameter of 1.8 cm and a length of 55 cm, with 16.5 cm of the tube being externally heated, has been found to be sufficient. This heated region is referred to as the reaction zone.

[0036] Generally, the gas flow may be adjusted within the range of about 0.76 L / min to about 1.14 L / min to allow the reaction mixture to reside in the reaction zone for 2-3 seconds. Both the flow rate and time in the reaction zone may be adapted to the length and diameter of the glass tube and the length of the reaction zone within the tube.

[0037] Additionally, it has been found that static mixing elements, such as glass wool plugs, may be introduced before or into the reaction zone, likely to have a positive impact on product purity due to improved mixing of the reactants.

[0038] Under these conditions, a reaction between (gaseous) germanium tetrachloride and hydrogen is initiated, rapidly leading to the production of the desired product trichlorogermane, thus producing a carrier gas stream containing gaseous trichlorogermane.

[0039] The carrier gas stream containing the gaseous trichlorogermane is then exposed to conditions, particularly suitable temperature and pressure, that allow for the collection of trichlorogermane and its separation from the gaseous extracts and by-products.

[0040] Generally, it is sufficient to operate at ambient pressure and cool to a temperature below 75°C, the boiling point of trichlorogermane. More specifically, the carrier gas stream containing gaseous trichlorogermane may be cooled to a temperature below 0°C, particularly below −30°C, which may be advantageous because decomposition to germanium chloride and hydrogen chloride can be suppressed at such low temperatures. In particular, cooling to a temperature below −71°C, the melting point of trichlorogermane, may be even more advantageous, with temperatures of −78°C or lower being even more advantageous. Therefore, the carrier gas stream containing gaseous trichlorogermane is generally cooled to a temperature between −80°C and 75°C, −80°C and −71°C, or −80°C and −30°C, particularly −78°C and 0°C, or −78°C and −30°C, or −78°C and −71°C. In other embodiments, it has been found that cooling using liquid nitrogen is practical, and the carrier gas stream containing gaseous trichlorogermane may be cooled to temperatures below −80° C., preferably below −120° C., and preferably above −200° C. Alternatively, the carrier gas stream containing gaseous trichlorogermane may be cooled to temperatures between −200° C. and 75° C., between −196° C. and −71° C., or between −196° C. and −30° C. [Prior art documents] [Non-patent literature]

[0041] [Non-Patent Document 1] Medicinal Chemistry,2009,5,382-384 [Non-patent document 2] CA Ros-kamp et al., “Encyclopedia of reagents for organic syntheses” [Non-patent document 3] C. Winkler, J. prakt. Chem.,1886, 34, 177-229 [Non-patent document 4] Georg Brauer, “Handbook of Preparative Inorganic Chemistry” [Non-Patent Document 5] LMDennis,Journal of Physical Chemistry,1926,30,1049-1054 [Non-patent document 6] CW Moulton et al., JACS, 1956, 78, 2702-2704 Summary of the Invention

[0042] In one embodiment, the method comprises: - providing a carrier gas stream comprising hydrogen; - contacting said carrier gas stream with a source of germanium tetrachloride (GeCl4) under conditions sufficient to at least partially saturate said carrier gas stream with germanium tetrachloride (GeCl4); - exposing the carrier gas stream to conditions sufficient to effect a reaction between germanium tetrachloride (GeCl4) and hydrogen (H2).

[0043] In this embodiment, contacting the carrier gas stream with the germanium tetrachloride (GeCl4) source may be performed by passing a stream of hydrogen through germanium tetrachloride at a temperature between 20°C and 100°C, particularly between 20°C and 60°C, or between 23°C and 40°C, before heating under inert conditions to a reaction temperature of 600°C or higher. Note that throughout this disclosure, the expression "under inert conditions" should be understood to mean the absence or at least minimization of the presence of both oxygen and water, and not to be broadly understood as the absence of any reactive components.

[0044] In another embodiment, the method comprises: - providing a carrier gas stream comprising hydrogen; providing a flow of germanium tetrachloride (GeCl4); - combining both a carrier gas stream and a germanium tetrachloride (GeCl4) stream; - exposing the combined carrier gas stream and germanium tetrachloride (GeCl4) stream to conditions sufficient to effect reaction of germanium tetrachloride (GeCl4) with hydrogen (H2).

[0045] In the two embodiments described above, the germanium tetrachloride (GeCl4) stream may be a liquid or a gas.

[0046] In the two embodiments described above, the steps of combining the carrier gas stream and the germanium tetrachloride (GeCl4) stream and exposing the combined carrier gas stream and germanium tetrachloride (GeCl4) stream to conditions sufficient to cause a reaction between germanium tetrachloride (GeCl4) and hydrogen (H2) are both performed simultaneously. This means that during combining the carrier gas stream and the germanium tetrachloride (GeCl4) stream, the temperature is preferably above 600°C and / or the pressure is preferably between 100 mbar and 10,000 mbar.

[0047] The step of combining both the carrier gas stream and the germanium tetrachloride (GeCl4) stream may be performed by injecting the germanium tetrachloride (GeCl4) stream into the carrier gas stream through a nozzle.

[0048] As discussed above, conditions sufficient to effect the reaction of germanium tetrachloride (GeCl4) with hydrogen (H2) include a reaction temperature above 600°C, particularly a reaction temperature between 600°C and 1200°C, or a reaction temperature between 1000°C and 1200°C, and / or a reaction pressure between 100 mbar and 10,000 mbar.

[0049] In the manufacturing method of any of the preceding claims, the carrier gas stream comprising gaseous germanium tetrachloride (GeCl4) and hydrogen is passed through a static mixing element before or while being exposed to conditions sufficient to cause reaction of the germanium tetrachloride (GeCl4) with hydrogen (H2).

[0050] In other, more specific embodiments, the reaction may be carried out under direct liquid injection conditions, where a gas stream (consisting of hydrogen, or a mixture of hydrogen and hydrogen chloride, or a mixture of hydrogen and an inert gas, or a mixture of hydrogen, hydrogen chloride, and an inert gas) is directed through a tube furnace and GeCl in pure form is introduced into the gas stream through a nozzle under conditions sufficient to allow reaction of germanium tetrachloride (GeCl) with the hydrogen.

[0051] Thus, the gas stream simultaneously performs the functions of reactant gas and carrier gas, reacting hydrogen with GeCl4 to form the product HGeCl3, and transporting it through the furnace to a location where it can be cooled and allowing the product to condense where it can be collected.

[0052] The condensation and reaction conditions are essentially the same as those described above, with a gas stream being bubbled through pure GeCl4 to create a GeCl4 saturated gas stream.

[0053] The present invention also relates to trichlorogermane (HGeCl3) directly obtainable by the production method of the present invention, and in particular to a crude trichlorogermane (HGeCl3) product containing at least 70% trichlorogermane, preferably at least 75%, more preferably at least 80% trichlorogermane (HGeCl3). DETAILED DESCRIPTION OF THE INVENTION

[0054] Working Example: Basic experimental procedure for the preparation of HGeCl3 from GeCl4 and H2: The corresponding parameter T B , J H2 , TR , t R , and the coolant / etc. used, see Table 1.

[0055] The tube furnace setup consisted of a 550 mm quartz glass tube (inner diameter: 18 mm). 165 mm of the tube was externally heated, defining the reaction zone. The gas flow was adjusted between 0.76 L / min and 1.14 L / min, allowing the reaction mixture to remain in the reaction zone for approximately 2–3 seconds. Furthermore, a glass wool plug introduced into the reaction zone was found to have a positive effect on product purity, likely due to better mixing of the reactants. Experiments using a glass wool plug are marked accordingly in Table 1.

[0056] GeCl4 is placed in a stainless steel bubbler and the bubbler is heated to a specific temperature, T B Preheated to. Pure hydrogen is fed into this bubbler at a flow rate of J H2 to generate a flow of H2 saturated with GeCl4. This GeCl4 / H2 mixture is heated to a specific temperature T R The mixture was passed through a glass tube placed in a tube furnace heated to RT. The reaction is R )went. · The reaction products were condensed at the tube outlet using either dry ice or liquid nitrogen as the condensing medium. In some experiments, a glass wool plug was introduced into the reaction zone to better mix the reactants. [Table 1]

[0057] The results of the study are summarized in Table 2.

[0058] · Care was taken when selecting parameters or experimental procedures to ensure that only one parameter was changed from one experiment to the next (Experiments 1–8). The gas phase concentration of GeCl4 was affected by the bubbler temperature. The first three experiments showed that a high hydrogen to GeCl4 ratio has a positive effect on the HGeCl3 content. The H2:GeCl4 ratio is calculated using the following parameters: Current flow rate J H2 *Reaction time t R = reaction volume H2, the reaction volume gives the amount of hydrogen used via the ideal gas equation p*V=n*R*T. The amount of GeCl4 is obtained by weighing the GeCl4 bubbler before and after the reaction. This can be explained by the fact that the reaction GeCl4 + H2 <-> HGeCl3 + HCl is an equilibrium reaction, which lies to the right with increasing hydrogen content. It has also been shown here that as the bubbler temperature increases, not only does GeCl4 consumption increase, but the amount of product isolated also increases, which is a direct effect of the increased evaporation rate of GeCl4 (due to higher vapor pressure / higher bubbler temperature). Experiments 3 and 4 were performed at a higher hydrogen flow rate J H2 It can be seen that the higher the temperature, the more negatively it affects the purity of the product. This can be explained by the shorter residence time of the reaction mixture in the reaction zone. At higher temperatures, the equilibrium is on the right side, so a longer stay in the high temperature reaction zone allows the equilibrium to be better established, towards the product side. At the same time, less GeCl4 is discharged and less crude product is isolated, which can be explained by the lower stock flow from the bubbler. Experiments 4 and 5 show that the lower the reaction temperature, the lower the content of HGeCl3. R The effect of the reaction GeCl4 + H2 <-> HGeCl3 + HCl on the HGeCl3 content of the crude product is clearly shown. Since the equilibrium for the reaction GeCl4 + H2 <-> HGeCl3 + HCl is to the right at high temperatures, the equilibrium is shifted towards the reactants GeCl4 and H2 at lower temperatures. Runs 1 and 7 show that with longer reaction times, the GeCl4 output increases (as expected), as well as the amount of crude product isolated (as expected). Interestingly, the purity also increases, likely due to the fact that forming GeCl2 (a by-product in the reaction) enters the collection vessel and reacts again with HCl (also a by-product of the reaction) to form HGeCl3. Runs 4 and 8 show that the temperature at which the product is condensed affects the release of GeCl4, the amount of crude product isolated, and the purity of the crude product. When the crude product is condensed at -196°C instead of -78°C, the release of GeCl4 increases, the amount of crude product isolated also increases, and the HGeCl3 content in the crude product also increases. The increased release is likely due to the fact that the significantly lower condensation temperature simultaneously generates a stronger negative pressure, thereby drawing more GeCl4 from the bubbler. The increased crude yield is directly attributable to the fact that the product vapor pressure is significantly lower at -196°C than at -78°C, and therefore less material is evacuated from the cold trap using the reaction gas flow from the collection vessel. The increased HGeCl3 content is likely the result of HCl freezing, which occurs at -196°C but not at -78°C. Since GeCl2 is considered one of the major impurities in the crude product, when it enters the collection vessel it may react with the HCl condensed therein to form HGeCl3, which may explain the increase in HGeCl3 content. Runs 4 and 6 show that the use of a glass wool plug in the reaction zone slightly increases the GeCl4 yield, the amount of crude product isolated, and the HGeCl3 content. The increase in GeCl4 output (and therefore crude yield) can be explained by statistical variations in adjusting the H2 flow rate, while the increase in HGeCl3 content can be the result of the glass wool plug ensuring better mixing of the reactants and better heat transfer from the heated outer tube wall to the center of the tube. In the final experiment, it may be seen that combining all parameters that showed a positive influence on the reaction during the first eight experiments leads to a further improvement in the results. Table 2

Claims

1. Germanium tetrachloride (GeCl ４ ) and hydrogen (H ２ ) by the gas-phase reaction of trichlorogermane (HGeCl ３ ) a manufacturing method for producing the compound.

2. The gas phase reaction proceeded in a furnace, and the hydrogen flux through the furnace was 0.5 L min －１ . cm －２ The method of claim 1, wherein:

3. The gas phase reaction proceeds in the furnace, and hydrogen (H ２ ) and germanium tetrachloride (GeCl ４ ) to hydrogen (H ２ ) and germanium tetrachloride (GeCl ４ 3. The method according to claim 1, wherein the molar ratio of 2 to 25 is supplied to the furnace.

4. The method according to any one of claims 1 to 3, wherein the reaction product obtained from the gas phase reaction is condensed at a temperature lower than -80°C and higher than -200°C.

5. - providing a carrier gas flow comprising hydrogen; - The carrier gas stream is made of germanium tetrachloride (GeCl ４ ) under conditions sufficient to at least partially saturate the carrier gas stream with germanium tetrachloride (GeCl ４ ) contacting the source of - The carrier gas flow is made up of germanium tetrachloride (GeCl ４ ) and hydrogen (H ２ and exposing the resulting mixture to conditions sufficient to effect reaction with The method according to any one of claims 1 to 4, comprising:

6. - providing a carrier gas flow comprising hydrogen; - germanium tetrachloride (GeCl ４ providing a flow of - the carrier gas flow and the germanium tetrachloride (GeCl ４ ) streams, and - germanium tetrachloride (GeCl ４ ) and hydrogen (H ２ and subjecting the combined carrier gas stream and germanium tetrachloride (GeCl) to conditions sufficient to effect a reaction with the ４ ) and a flow of The method according to any one of claims 1 to 5, comprising:

7. The germanium tetrachloride (GeCl ４ 7. The method according to claim 1, wherein the flow of the component (a) is a liquid or a gas.

8. the carrier gas flow and the germanium tetrachloride (GeCl ４ ) is mixed with the germanium tetrachloride (GeCl ４ ) and hydrogen (H ２ and subjecting the combined carrier gas stream and germanium tetrachloride (GeCl) to conditions sufficient to effect a reaction with the ４ The method of any one of claims 1, 6 and 7, wherein the step of exposing to a flow of

9. The carrier gas flow and the germanium tetrachloride (GeCl ４ ) is mixed with the germanium tetrachloride (GeCl ４ 9. The method of any one of claims 1 and 6 to 8, wherein the method is carried out by injecting a stream of methyl methyl ether into the carrier gas stream through a nozzle.

10. Germanium tetrachloride (GeCl ４ ) hydrogen (H ２ The method of any one of claims 1 to 9, wherein the conditions sufficient to effect a reaction with 2-(2-methyl-2-propanol)-2-one include a reaction temperature of greater than 600°C.

11. The method according to any one of claims 1 to 10, wherein the reaction temperature is 600°C to 1200°C.

12. The method according to any one of claims 1 to 11, wherein the reaction temperature is 1000°C to 1200°C.

13. Germanium tetrachloride (GeCl ４ ) hydrogen (H ２ 13. The process of any one of claims 1 to 12, wherein the conditions sufficient to effect reaction with 2-(2-methyl-2-propanol)-2-hydroxybenzoyl) include a reaction pressure of from 100 mbar to 10,000 mbar.

14. The process according to any one of claims 1 to 13, wherein the reaction pressure is from 800 to 2000 mbar.

15. Germanium tetrachloride (GeCl ４ 15. The method of claim 1, wherein a gas mixture of the hydroxybenzoate and the carrier gas is produced.

16. The germanium tetrachloride (GeCl ４ ) in gaseous germanium tetrachloride (GeCl ４ ), and a carrier gas flow is introduced into the gaseous germanium tetrachloride (GeCl ４ 16. The method of claim 1, wherein the molten metal is exposed to a temperature and pressure sufficient to pass the molten metal through a process known in the art.

17. The carrier gas flow was gaseous germanium tetrachloride (GeCl ４ 4. Liquid germanium tetrachloride (GeCl) exposed to conditions sufficient to allow the generation of a stream of carrier gas containing ４ 17. The method according to claim 1, wherein the molten metal is passed through a molten metal.

18. The method according to any one of claims 1 to 17, wherein the carrier gas is an inert gas or hydrogen.

19. The method of any one of claims 1 to 18, wherein the carrier gas is selected from nitrogen, hydrogen, helium, neon, argon, hydrogen chloride, xenon, or a combination thereof.

20. Germanium tetrachloride (GeCl ４ 20. The method according to claim 1, wherein the carrier gas containing the fluorine-containing compound is mixed with hydrogen.

21. The method according to any one of claims 1 to 20, wherein the carrier gas is hydrogen.

22. A process according to any one of the preceding claims, in which a stream of hydrogen is passed over germanium tetrachloride at a temperature between 20°C and 100°C, which is then heated to a reaction temperature of 600°C or above under inert conditions.

23. The gas stream is passed through a cold trap at a temperature below −50° C. to remove the solid product trichlorogermane (HGeCl ３ 23. The method according to claim 1, wherein

24. Gaseous germanium tetrachloride (GeCl ４ ) and hydrogen, and ４ ) and hydrogen (H ２ 24. The process of claim 1, wherein the cellulose acetate solution is passed through a static mixing element before or while being exposed to conditions sufficient to effect reaction with the cellulose acetate solution.

25. Trichlorogermane (HGeCl) directly obtained by the method according to any one of claims 1 to 24 ３ ).

26. At least 80% trichlorogermane (HGeCl ３ 26. The method of claim 1, wherein the trichlorogermane (HGeCl) is directly obtained by the method of claim 1. ３ ) Crude product.

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