Method for preparing high-purity germane-73 isotope by using amorphous germane-73 dioxide
High-purity germanium-73 isotopes were prepared by medium-temperature calcination and multi-stage hydrogen flow regulation reduction treatment of germanium dioxide-73, which solved the problem of insufficient purity in the existing technology and achieved the high purity requirements of quantum computing chip substrates.
Patent Information
- Application Number
- CN202511274125.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-08
- Publication Date
- 2026-01-06
AI Technical Summary
Existing technologies make it difficult to prepare high-purity germanium-73 isotopes that meet the requirements of quantum computing research, especially elemental germanium with a purity of ≥99.99995%.
High-purity germanium-73 isotopes were obtained by calcining amorphous germanium dioxide at 450℃ to 600℃ and then reducing it using a multi-stage heating and dynamic hydrogen flow rate adjustment strategy. The isotopes were then further purified by zone melting.
The purity of germanium-73 isotope reached 99.99995%, meeting the requirements of quantum computing chip substrate coating and improving the accuracy of product purity analysis.
Smart Images
Figure CN121272201A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of quantum computing research and relates to the preparation technology of germanium-73 ingots, specifically to a method for preparing high-purity germanium-73 isotopes using amorphous germanium dioxide-73. Background Technology
[0002] High-purity germanium-73, used as a coating for chip substrates, can improve the decoherence time of qubits and is a key and urgently needed material in the field of quantum computing research. Currently, the successfully isolated germanium-73 tetrafluoride cannot be used directly and needs to be converted into high-purity germanium-73 isotope materials.
[0003] Currently, there has been extensive research on the preparation of high-purity germanium through hydrogen reduction of germanium dioxide, but the demand for high-purity germanium-73 isotopes as a special semiconductor material for quantum information chips is still in its infancy.
[0004] Germanium dioxide prepared by hydrolysis and neutralization was reduced by hydrogen after high-temperature calcination, and the highest purity of the obtained elemental germanium was 99.9999%. The purity was calculated by the difference method (100% minus the content of 11 metal elements specified in the national standard). This calculation method yielded a higher purity of elemental germanium than the true value and could not meet the requirement of ≥99.99995% purity of germanium materials in the field of quantum computing research. Summary of the Invention
[0005] To address the technical problem that existing methods for preparing elemental germanium cannot achieve the purity requirement of ≥99.99995% for materials used in quantum computing research, this invention discloses a method for preparing high-purity germanium-73 isotopes using amorphous germanium dioxide-73. The method includes the following steps: Step 2: Calcining germanium dioxide-73 at 450℃~600℃ to obtain amorphous germanium dioxide-73; Step 3: Using a multi-stage heating and dynamic hydrogen flow rate adjustment strategy, amorphous germanium dioxide-73 is reduced in a hydrogen atmosphere to obtain crude germanium-73 isotope. The crude germanium-73 isotope is then subjected to zone melting to obtain high-purity germanium-73 isotope.
[0006] Furthermore, in step two, the calcination temperature is 500℃~600℃.
[0007] Furthermore, the specific surface area of the amorphous germanium dioxide-73 is 10.588 ± 1.0 m². 2 / g, with a bulk density of 1.05–1.2 g / ml.
[0008] Furthermore, the multi-stage heating and dynamic hydrogen flow regulation strategy is a three-stage control strategy, including: First stage: Using the first hydrogen flow rate and the first heating rate, the reaction system is heated from room temperature to 550°C; Second stage: Using a second hydrogen flow rate and a second heating rate, the temperature is raised from 550℃ to 650℃~700℃ and held for 1~3 hours, wherein the first hydrogen flow rate is < the second hydrogen flow rate; The third stage involves raising the temperature from 650℃~700℃ to 950℃ and maintaining it in an inert gas atmosphere for 20~30 minutes to complete the reduction reaction.
[0009] Furthermore, the first heating rate is greater than the second heating rate.
[0010] Furthermore, the first hydrogen flow rate is 640–720 mL / min, and the second hydrogen flow rate is 720–1020 mL / min.
[0011] Furthermore, the reduction reaction is carried out in a tube furnace.
[0012] Furthermore, prior to calcination, it also includes: Step 1: Using germanium tetrafluoride-73 as raw material, crude germanium dioxide-73 is prepared by neutralization. The crude germanium dioxide-73 is then washed and dried to obtain germanium dioxide-73 for calcination.
[0013] Furthermore, in step one, the neutralization method includes: Step 11: Dissolve germanium tetrafluoride-73 in water to carry out a hydrolysis reaction, generating a mixed solution containing germanium dioxide-73 and fluorogermanic acid-73; Step 1 and Step 2: Add ammonia water to the mixture to neutralize fluorogermanic acid-73 with ammonia water to form a soluble ammonium salt; Step 13: Perform solid-liquid separation on the mixture after the neutralization reaction, collect the solid precipitate, and wash and dry it in sequence to obtain germanium dioxide-73.
[0014] Furthermore, the purity of the high-purity germanium-73 isotope is ≥99.99995%.
[0015] The method of this invention involves calcining crude germanium dioxide-73 at a medium temperature of 450℃ to 600℃ to remove fluorine-containing impurities, obtaining amorphous germanium dioxide-73. Then, a hydrogen reduction reaction is carried out using a multi-stage heating and dynamic hydrogen flow rate adjustment strategy, followed by ingot casting to obtain elemental germanium-73. This germanium-73 preparation process effectively removes impurities from the germanium dioxide-73 generated during the neutralization process by increasing the medium-temperature calcination and setting specific calcination conditions. The multi-stage heating and dynamic hydrogen flow rate adjustment strategy effectively improves the reduction yield. The product, after zone melting, yields germanium-73 with a purity ≥99.99995%, meeting the requirements for chip substrate coatings in quantum computing research. Furthermore, the purity calculation of germanium-73 prepared by this invention is obtained by subtracting 28 characteristic metal elements from 100%, which greatly improves the accuracy of product purity analysis. Attached Figure Description
[0016] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0017] Figure 1 This is a flowchart of the method for preparing high-purity germanium-73 isotopes using amorphous germanium dioxide-73 according to the present invention; Figure 2 This invention describes the process flow for preparing germanium dioxide-73 before calcination using germanium tetrafluoride-73. Detailed Implementation
[0018] The embodiments of this application will now be described in detail with reference to the accompanying drawings.
[0019] The following specific examples illustrate the implementation of this application. Those skilled in the art can easily understand other advantages and effects of this application from the content disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. This application can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of this application. It should be noted that, in the absence of conflict, the following embodiments and features of the embodiments can be combined with each other. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0020] This invention discloses a method for preparing high-purity germanium-73 isotopes using amorphous germanium dioxide-73, see [link to relevant documentation]. Figure 1 As shown, the method includes the following steps: Step 2: Calcining germanium dioxide-73 at 450℃~600℃ to obtain amorphous germanium dioxide-73; Step 3: Using a multi-stage heating and dynamic hydrogen flow rate adjustment strategy, amorphous germanium dioxide-73 is reduced in a hydrogen atmosphere to obtain crude germanium-73 isotope. The crude germanium-73 isotope is then subjected to zone melting to obtain high-purity germanium-73 isotope.
[0021] The chemical formula for the hydrogen reduction reaction is: 73 GeO2 + 2H2 = 73 The high-purity germanium-73 isotope obtained by Ge + 2H2O has a purity ≥ 99.99995%.
[0022] The purity of the high-purity germanium-73 isotope of the present invention, as shown in Table 1 below, is obtained by subtracting the sum of the contents of 28 metal elements from 100%. Compared with the purity obtained by subtracting the contents of 11 metal elements as specified in the national standard, the accuracy of product purity analysis has been greatly improved.
[0023] Table 1: Purity and Analytical Impurities of Depleted Germanium-73 Product
[0024] Furthermore, research has shown that the main function of calcining germanium dioxide is to transform its crystal form, typically forming amorphous (i.e., non-crystalline) and hexagonal crystals. In the hydrogen reduction of germanium dioxide to prepare germanium, the non-crystalline form requires less energy and is easier to transform, considering the energy required for hydrogen reduction. This invention compares the specific surface area and hydrogen reduction effect of germanium dioxide after calcination at different temperatures, and the results are shown in Table 2 below: Table 2: Results of germanium dioxide calcined at different temperatures
[0025] According to the results in Table 2 above, germanium dioxide obtained by medium-temperature calcination at 450℃ to 600℃ has better surface properties, with a specific surface area 7.14 times that of germanium dioxide calcined at 950℃, and a bulk density about half that of the latter. Comparative hydrogen reduction experiments show that the hydrogen reduction effect of germanium dioxide obtained by medium-temperature calcination is better than that of germanium dioxide obtained by high-temperature calcination. Furthermore, the yield after hydrogen reduction is higher for germanium dioxide products obtained by both medium-temperature calcination and hydrogen reduction than that obtained by high-temperature calcination.
[0026] This invention utilizes the boiling point of ammonium germanate, a byproduct of hydrolysis and neutralization, which is 380℃. Experiments were conducted to verify the results at calcination temperatures ranging from 450℃ to 600℃ to maintain an amorphous crystalline structure. Temperatures of 400℃, 500℃, 600℃, and 700℃ were selected for testing. Specific surface area and material morphology were measured, and hydrogen reduction experiments were performed to compare the reduction effect. 100g samples were calcined in a muffle furnace at 400℃, 500℃, 600℃, and 700℃ for 2 hours. The specific surface area and morphology of the calcined materials were measured, and the results are shown in Table 3 below. Table 3: Results of obtaining amorphous germanium dioxide by calcining germanium dioxide at different temperatures
[0027] As shown in Table 3 above, volatile components are still generated during the hydrogen reduction process after germanium dioxide is calcined at 400℃. Analysis shows that 400℃ is close to the boiling point of fluorine-containing substances, indicating that the removal of fluorine compounds from germanium dioxide is incomplete at this temperature, resulting in a low hydrogen reduction yield. After calcination at 700℃, the crystal structure of germanium dioxide changes to a hexagonal crystal form. Under unchanged hydrogen reduction conditions, a relatively large amount of gaseous germanium monoxide is generated during the process, resulting in the loss of germanium element and thus a low overall yield.
[0028] In summary, the optimal processing technology for germanium-73 was determined to be: after drying the germanium-73 prepared from germanium tetrafluoride-73, the germanium-73 needs to be calcined at a temperature of 500℃~600℃ for 2 hours to achieve the best results. This ensures both the high resistivity of the reduced germanium-73 ingot and the high yield, while avoiding the loss of germanium-73 element.
[0029] After calcination, the obtained amorphous germanium dioxide-73 was subjected to hydrogen reduction treatment. The hydrogen reduction reaction began when the reduction temperature reached 550℃–650℃. However, when the temperature was subsequently raised to 700℃ and above, if the hydrogen flow rate was insufficient, highly volatile germanium monoxide (GNO3) would be generated in the system. 73 The gaseous product (GeO) is discharged from the reaction system along with the carrier gas or insufficiently circulated hydrogen flow, resulting in irreversible loss of germanium-73, reducing product yield, and potentially contaminating the equipment. Therefore, the multi-stage heating and dynamic hydrogen flow regulation strategy selected in this invention is a three-stage control strategy, specifically including: First stage: Using the first hydrogen flow rate and the first heating rate, the reaction system is heated from room temperature to 550°C; Second stage: Using a second hydrogen flow rate and a second heating rate, the temperature is raised from 550℃ to 650℃~700℃ and held for 1~3 hours, wherein the first hydrogen flow rate is < the second hydrogen flow rate; The third step involves raising the temperature from 650℃~700℃ to 950℃ and maintaining this temperature in an inert gas atmosphere for 20~30 minutes to complete the reduction reaction. Maintaining the reaction in an inert gas atmosphere, such as nitrogen, further prevents the formation of germanium monoxide-73 during the reaction. 73 GeO) gaseous products.
[0030] Furthermore, the first heating rate is greater than the second heating rate. The first heating rate can be set to 5-8℃ / min, and the second heating rate can be set to 3-5℃ / min.
[0031] Furthermore, the first hydrogen flow rate can be selected as 640–720 mL / min, and the second hydrogen flow rate is 720–1020 mL / min, to prevent the formation and loss of germanium monoxide-73.
[0032] During the hydrogen reduction reaction, when the temperature is raised to the second stage, in order to ensure that the reaction atmosphere is strongly reducing and to suppress... 73 The generation and volatilization of GeO require increasing the hydrogen flow rate during this stage to ensure sufficient reduction in the mid-temperature zone under a adequate hydrogen atmosphere, avoiding prolonged high-temperature stays for "supplementary reduction".
[0033] In this invention, by controlling the flow rate of the hydrogen atmosphere and the coordinated matching of the heating program, germanium monoxide-73 (GNO3) is effectively suppressed in the high-temperature stage. 73 The generation and volatilization of GeO were investigated. Experiments showed that when the hydrogen flow rate was below 400 mL / min and the temperature exceeded 700℃, gaseous GeO could be detected, and the germanium yield decreased by more than 8%. However, by adopting the hydrogen flow rate (≥600 mL / min) and the medium-temperature insulation strategy in the second stage recommended by this invention, the germanium recovery rate remained stable at over 98%, significantly improving the process economy and product consistency.
[0034] Furthermore, before calcination, ginseng Figure 1 and Figure 2 As shown, it also includes: Step 1: Using germanium tetrafluoride-73 as raw material, crude germanium dioxide-73 is prepared by neutralization. The crude germanium dioxide-73 is then washed and dried to obtain germanium dioxide-73 for calcination.
[0035] Furthermore, in step one, the neutralization method includes: Step 1: Dissolve germanium tetrafluoride-73 in water to carry out a hydrolysis reaction, generating a mixed solution containing germanium dioxide-73 and fluorogermanic acid-73.
[0036] The chemical formula for the hydrolysis reaction is: 3 73 GeF4 + 2H2O = 73GeO2+2H2 73 GeF6.
[0037] Step 1: Add ammonia to the mixture to neutralize fluorogermanic acid-73 with the ammonia to form a soluble ammonium salt.
[0038] Chemical formula for neutralization reaction: H2 73 GeF6 + 6NH4OH = 73 Ge(OH)4 + 6 NH4F + 2H2O.
[0039] Step 13: Perform solid-liquid separation on the mixture after the neutralization reaction, collect the solid precipitate, and wash and dry it in sequence to obtain germanium dioxide-73.
[0040] Equation for the decomposition reaction: 73 Ge(OH)4= 73 GeO2 + 2H2O.
[0041] The invention utilizes the above method to prepare high-purity germanium-73 isotopes with a purity ≥99.99995%, as shown in Examples 1 and 2 below: Example 1: 72.9g of amorphous germanium dioxide-73, calcined at 500℃ for 2h, was evenly spread in a graphite boat with a material thickness of 11mm. Three temperature zones were set for heating. The hydrogen flow rate was adjusted to 640ml / min, and the heating rate was 5℃ / min, raising the temperature from room temperature to 550℃. The hydrogen flow rate was then adjusted to 740ml / min, and the heating rate was 3℃ / min, raising the temperature from 550℃ to 650℃, and holding at 650℃ for 120min. Subsequently, the temperature was raised to 950℃, and the nitrogen flow rate was adjusted to 2L / min to supplement the nitrogen supply. The temperature was held for another 20min. After cooling to room temperature, the germanium-73 ingot was weighed and found to be 49.74g. The germanium-73 recovery rate was calculated to be 98.1%, and the purity reached 99.99995%.
[0042] Example 2: 99.7g of amorphous germanium dioxide-73, calcined at 600℃ for 2h, was evenly spread in a graphite boat with a material thickness of 12mm. Three temperature zones were set for heating. The hydrogen flow rate was adjusted to 700ml / min, and the heating rate was 8℃ / min, raising the temperature from room temperature to 550℃; the hydrogen flow rate was then adjusted to 1000ml / min, and the heating rate was 5℃ / min, raising the temperature from 550℃ to 700℃. The temperature was held at 700℃ for 120min, then raised to 950℃. The nitrogen flow rate was adjusted to 3L / min, and nitrogen was introduced to supplement the gas flow. The temperature was held for another 30min. After cooling to room temperature, the germanium-73 ingot was weighed and found to be 68.14g. The germanium-73 recovery rate was calculated to be 98.3%, and the purity reached 99.99996%.
[0043] The method of this invention involves calcining crude germanium dioxide-73 at a temperature of 450℃ to 600℃ to remove fluorine-containing impurities, obtaining amorphous germanium dioxide-73. This is followed by hydrogen reduction and ingot casting to obtain elemental germanium-73. The preparation process of this germanium-73 effectively removes fluorine-containing impurities generated during the neutralization process by increasing calcination and setting specific calcination conditions. Furthermore, the reduction yield is effectively improved by employing a multi-stage heating and dynamic hydrogen flow rate adjustment strategy. The product, after zone melting, yields germanium-73 with a purity ≥99.99995%, meeting the requirements for use in chip substrate coatings.
[0044] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, various modifications and variations can be made to the embodiments of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for the production of high purity germanium-73 isotope from amorphous germanium dioxide-73, characterized in that, The method comprises the following steps: The amorphous germanium dioxide-73 is obtained by calcining germanium dioxide-73 at 450-600℃; The germanium-73 isotope crude product is obtained by reducing the amorphous germanium dioxide-73 in a hydrogen atmosphere by using a multi-stage temperature rising and dynamic hydrogen flow adjustment strategy, and the high-purity germanium-73 isotope is obtained by subjecting the germanium-73 isotope crude product to zone melting.
2. The method of claim 1, wherein the method is characterized by, The calcination temperature is 500-600℃.
3. The method of producing high purity germanium-73 isotope from amorphous germanium dioxide-73 according to claim 1 or 2, characterized in that, The amorphous germanium dioxide-73 has a specific surface area of 10.588 ± 1.0 m 2 / g and a bulk density of 1.05 to 1.2 g / ml.
4. The method of claim 1, wherein the method is characterized by, The multi-stage temperature rising and dynamic hydrogen flow adjustment strategy is a three-stage adjustment strategy, which comprises the following steps: In the first stage, the reaction system is raised from room temperature to 550℃ at a first hydrogen flow and a first temperature rising rate; In the second stage, the temperature is raised from 550℃ to 650-700℃ at a second hydrogen flow and a second temperature rising rate, and the temperature is kept for 1-3 hours, wherein the first hydrogen flow is less than the second hydrogen flow; In the third stage, the temperature is raised from 650-700℃ to 950℃, and the reduction reaction is completed in an inert gas atmosphere for 20-30 minutes.
5. The method of claim 4, wherein the method is characterized by, The first temperature rising rate is greater than the second temperature rising rate.
6. The method of claim 4, wherein the method is characterized by, The first hydrogen flow is 640-720 mL / min, and the second hydrogen flow is 720-1020 mL / min.
7. The method of claim 4, wherein the method is characterized by, The reduction reaction is carried out in a tube furnace.
8. The method of claim 1, wherein the method is characterized by: Before calcination, the method further comprises the following steps: The germanium dioxide-73 crude product is prepared from germanium tetrafluoride-73 by a neutralization method, and the germanium dioxide-73 crude product is washed and dried in sequence to obtain the germanium dioxide-73 used for calcination.
9. The method of claim 8, wherein the method is characterized by, The neutralization method comprises the following steps: The germanium tetrafluoride-73 is dissolved in water to generate a mixed solution containing germanium dioxide-73 and germanate-73 by a hydrolysis reaction; Ammonia is added to the mixed solution to generate a soluble ammonium salt by a neutralization reaction between the germanate-73 and the ammonia; The mixture after the neutralization reaction is subjected to solid-liquid separation, and the solid precipitate is collected and washed and dried in sequence to obtain the germanium dioxide-73.
10. The method of claim 1, wherein the method is characterized by, The purity of the high-purity germanium-73 isotope is greater than or equal to 99.99995%.