TW202011028A - Method for determining oxygen or carbon in semiconductor material - Google Patents

Method for determining oxygen or carbon in semiconductor material Download PDF

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TW202011028A
TW202011028A TW108130988A TW108130988A TW202011028A TW 202011028 A TW202011028 A TW 202011028A TW 108130988 A TW108130988 A TW 108130988A TW 108130988 A TW108130988 A TW 108130988A TW 202011028 A TW202011028 A TW 202011028A
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TWI716090B (en
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迪特 雷斯曼
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德商世創電子材料公司
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44Sample treatment involving radiation, e.g. heat
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3563Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67242Apparatus for monitoring, sorting or marking
    • H01L21/67253Process monitoring, e.g. flow or thickness monitoring

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Abstract

A method for determining the content of oxygen or carbon in semiconductor material by gas fusion analysis comprising cleaning a crucible and a test sample of the semiconductor material by inductively heating the test sample in the crucible to a temperature of not less than 1300 DEG C in a stream having a composition of nitrogen or a mixture of nitrogen and at least one rare gas; and determining the content of oxygen or carbon in the test sample of semiconductor material in a measuring chamber (2) of a measuring device (100), comprising inductively heating in the measuring chamber (2) the test sample in a gas stream having said composition and melting the test sample in the crucible (1); reacting oxygen contained in the test sample with carbon or reacting carbon contained in the test sample with oxygen to form at least one oxidation product; and determining the amount of the at least one oxidation product and using the amount of the at least one oxidation product as a measure of the content of oxygen or carbon contained in the test sample.

Description

測定半導體材料中的氧或碳的方法Method for determining oxygen or carbon in semiconductor materials

本發明的主題是一種藉由氣體熔融分析(gas fusion analysis,GFA)來測定半導體材料中的氧或碳的方法。The subject of the present invention is a method for determining oxygen or carbon in semiconductor materials by gas fusion analysis (GFA).

GFA是一種特別用於定量測定(quantitatively determine)半導體材料之測試樣品中的氧或碳含量的方法。為此目的,將測試樣品熔化並將其中所含的氧或碳轉化為化合物,透過光譜法來定量測定所述化合物。GFA is a method especially used to quantitatively determine the content of oxygen or carbon in test samples of semiconductor materials. For this purpose, the test sample is melted and the oxygen or carbon contained therein is converted into a compound, and the compound is quantitatively determined by spectrometry.

先前技術/問題Previous technology/problem

用於測定太陽能電池的矽中的氧或碳的分析系統可在市場上獲得(S.阪倉『測定太陽能電池的矽中的氧與碳』技術期刊Readout、英文版第14號、第66至69頁、2011年2月(S. Sakakura,“Determination of Oxygen and Carbon of Silicon for Solar Cell” Readout, English Edition No.14, pages 66-69, February 2011))。此二種元素係經由GFA確定,因此需要具有不同測量程序的單獨裝置,其包括坩堝及測試樣品的複雜多階段清潔(complex multi-stage cleaning)。清潔測試樣品的目的是從測試樣品的表面除去外來材料(foreign material),以確保隨後測定的氧或碳的含量可歸於測試樣品的內部(整體(bulk))。Analytical systems for measuring oxygen or carbon in silicon of solar cells are available on the market (S. Sakakura "Determination of Oxygen and Carbon in Silicon of Solar Cells" technical journal Readout, English version No. 14, 66 to 69 pages, February 2011 (S. Sakakura, "Determination of Oxygen and Carbon of Silicon for Solar Cell" Readout, English Edition No. 14, pages 66-69, February 2011). These two elements are determined by GFA, so separate devices with different measurement procedures are required, including complex multi-stage cleaning of crucibles and test samples. The purpose of cleaning the test sample is to remove foreign material from the surface of the test sample to ensure that the content of oxygen or carbon subsequently determined can be attributed to the inside of the test sample (bulk).

DE 10 2014 217 514 A1描述一種基於氣體熔融分析來測定半導體材料的測試樣品中的碳的方法。DE 10 2014 217 514 A1 describes a method for determining carbon in test samples of semiconductor materials based on gas fusion analysis.

期望改善藉由氣體熔融分析對半導體材料中的氧或碳的測定。It is desirable to improve the determination of oxygen or carbon in semiconductor materials by gas fusion analysis.

該任務係藉由一種藉由氣體熔融分析來測定半導體材料中的氧或碳含量的方法來解決,該方法包含: 在具有氮氣組成或氮氣與至少一種稀有氣體的混合物的氣流中感應加熱(inductively heating)坩堝中的半導體材料的測試樣品至不低於1300°C的溫度,從而清潔坩堝與半導體材料的測試樣品;以及 在測量裝置的測量室中測定半導體材料的測試樣品中的氧或碳的含量,這包含在測量室中在具有所述組成的氣流中感應加熱測試樣品並將坩堝中的測試樣品熔化;使測試樣品中所含有的氧與碳反應或使測試樣品中所含有的碳與氧反應以形成至少一種氧化產物;測定所述至少一種氧化產物的量並使用該至少一種氧化產物的量作為測試樣品中所含氧或碳的含量的量度(measure)。This task is solved by a method for determining the oxygen or carbon content in semiconductor materials by gas fusion analysis. The method includes: Inductively heating the test sample of the semiconductor material in the crucible to a temperature of not less than 1300°C in a gas stream having a nitrogen composition or a mixture of nitrogen and at least one rare gas, thereby cleaning the test sample of the crucible and semiconductor material; as well as The content of oxygen or carbon in the test sample of the semiconductor material is determined in the measurement chamber of the measurement device, which involves inductively heating the test sample in the gas flow with the composition in the measurement chamber and melting the test sample in the crucible; making the test Oxygen contained in the sample reacts with carbon or reacts carbon contained in the test sample with oxygen to form at least one oxidation product; determine the amount of the at least one oxidation product and use the amount of the at least one oxidation product as the test sample A measure of the content of oxygen or carbon contained.

根據本發明,在由氮氣組成的氣流中或由氮氣與至少一種惰性氣體的混合物(例如氮氣與氬氣的混合物)組成的氣流中將坩堝中的測試樣品以及坩堝本身(若有需要)感應加熱到至少1300°C的溫度,從而同時清潔坩堝與測試樣品。在氮氣的存在下,可非常容易地從測試樣品的表面除去含有氧或碳的雜質,使得測量結果不被附著在表面上的外來材料所誤導。另外,氮的存在係引起半導體材料的氮化(nitriding),這有利於外來材料從測試樣品內部擴散到其表面。According to the invention, the test sample in the crucible and the crucible itself (if required) are induction heated in a gas flow consisting of nitrogen or a mixture of nitrogen and at least one inert gas (eg a mixture of nitrogen and argon) To a temperature of at least 1300°C to clean the crucible and test sample at the same time. In the presence of nitrogen, impurities containing oxygen or carbon can be easily removed from the surface of the test sample, so that the measurement results are not misled by foreign materials adhering to the surface. In addition, the presence of nitrogen causes nitriding of semiconductor materials, which facilitates the diffusion of foreign materials from the inside of the test sample to its surface.

如果要用於感應加熱以進行清潔的測試樣品係由半導體材料製成,而該半導體材料由於未摻雜或僅輕微摻雜而不具有足夠的固有導電性(intrinsic conductivity),則例如經由來自鹵素燈的輻射而將測試樣品預熱至300°C至500°C的溫度。或者,將測試樣品補充額外的半導體材料,該額外的半導體材料具有足夠的固有導電性且其氧與碳的含量是已知的,並且在稀釋到測試樣品的體積中之後,與測試樣品的預期含量相比較是低的。較佳地,由額外的半導體材料添加的已知的碳含量係小於測試樣品的預期碳含量的10%。用於補充而添加的半導體材料的比電阻(specific electrical resistance)應較佳不超過0.5歐姆·公分(Ohmcm)。然後,此種測試樣品也可被感應加熱到目標溫度以進行清潔而沒有任何問題。如果坩堝是由碳製成的,則不需要採取該等特殊的預防措施。在此情況下,坩堝也被感應加熱,且在此過程中,在坩堝內部的測試樣品也被預熱。在此情況下,只能測定熔化樣品的氧含量。If the test sample to be used for induction heating for cleaning is made of a semiconductor material that does not have sufficient intrinsic conductivity because it is undoped or only slightly doped, for example, via halogen The radiation of the lamp preheats the test sample to a temperature of 300°C to 500°C. Alternatively, the test sample is supplemented with additional semiconductor material that has sufficient intrinsic conductivity and whose oxygen and carbon content is known, and after dilution into the volume of the test sample, the expected value of the test sample The content is relatively low. Preferably, the known carbon content added by the additional semiconductor material is less than 10% of the expected carbon content of the test sample. The specific electrical resistance of the semiconductor material added for supplementation should preferably not exceed 0.5 ohm·cm (Ohmcm). Then, such test samples can also be induction heated to the target temperature for cleaning without any problems. If the crucible is made of carbon, these special precautions are not necessary. In this case, the crucible is also heated by induction, and in the process, the test sample inside the crucible is also preheated. In this case, only the oxygen content of the molten sample can be determined.

較佳地,在清潔過程中將測試樣品加熱到測試樣品開始在表面上熔化的溫度。例如,可使用IR溫度計而無接觸地測量測試樣品的溫度。清潔的持續時間係尤其取決於測試樣品的重量及坩堝的污染程度,且例如可憑經驗確定。為此,在不同時間段清潔測試樣品,並在清潔後檢查其表面。Preferably, the test sample is heated to a temperature at which the test sample begins to melt on the surface during the cleaning process. For example, an IR thermometer can be used to measure the temperature of the test sample without contact. The duration of cleaning depends inter alia on the weight of the test sample and the degree of contamination of the crucible, and can be determined empirically, for example. To this end, the test sample is cleaned at different time periods and the surface is inspected after cleaning.

根據本發明的一個實施態樣,坩堝與測試樣品的清潔係在測定氧或碳含量的測量裝置外部進行。在此情況下,在清潔之後,坩堝與坩堝內的測試樣品係在惰性氣體(例如氬氣)下被輸送到測量裝置中。According to an embodiment of the present invention, the cleaning of the crucible and the test sample is performed outside the measuring device for determining the content of oxygen or carbon. In this case, after cleaning, the crucible and the test sample in the crucible are transported to the measuring device under an inert gas (for example, argon).

根據本發明的另一個較佳實施態樣,坩堝與測試樣品的清潔係在測量裝置中進行(原位清潔(in situ cleaning)),在所述測量裝置中在清潔後測定測試樣品中的氧或碳的含量。該實施態樣具有的優點是,在開始測定氧或碳的含量之前,不再需要冷卻及輸送測試樣品。According to another preferred embodiment of the present invention, the cleaning of the crucible and the test sample is performed in a measuring device (in situ cleaning), and the oxygen in the test sample is determined in the measuring device after cleaning Or carbon content. This embodiment has the advantage that it is no longer necessary to cool and transport the test sample before starting to determine the oxygen or carbon content.

在原位純化(in situ purification)的過程中,作為外來物質以結合形式(in bound form)黏附在測試樣品上的氧係被用碳轉化為至少一種氧化產物,例如一氧化碳。有利的是,在氧化成二氧化碳後如果合適,藉由紅外光譜法(infrared spectrometry)或其他氣體分析方法來分析該氧化產物。在該分析過程中,可測定測試樣品之表面上的氧濃度。當指示氧化產物之存在的測量信號的強度在最初超過預定的下閾值(lower threshold)之後已經返回到該閾值時,則認為原位清潔完成。較佳在測定其氧或碳含量之前不冷卻測試樣品。During the in-situ purification process, the oxygen system adhering to the test sample as a foreign substance in bound form is converted with carbon to at least one oxidation product, such as carbon monoxide. Advantageously, after oxidation to carbon dioxide, if appropriate, the oxidation product is analyzed by infrared spectrometry or other gas analysis methods. During this analysis, the oxygen concentration on the surface of the test sample can be determined. When the intensity of the measurement signal indicating the presence of the oxidation product has returned to the predetermined lower threshold after initially exceeding the predetermined lower threshold, it is considered that the in-situ cleaning is completed. It is preferable not to cool the test sample before determining its oxygen or carbon content.

為了測定氧或碳的含量,將坩堝中的測試樣品在氣流中感應加熱並熔化,所述氣流的組成係對應於清潔坩堝與測試樣品期間的氣流的組成。測試樣品內所含有的氧係被用碳轉化或測試樣品中所含有的碳係被用氧轉化為至少一種氧化產物。如果需要,在氧化成二氧化碳後,較佳藉由紅外光譜法來分析該氧化產物,並測定測試樣品中的氧或碳的濃度。可使用另一種氣體分析方法來代替紅外光譜法,例如使用熱導檢測器(thermal conductivity detector)(WLD)的氣體分析方法。In order to determine the content of oxygen or carbon, the test sample in the crucible is heated and melted by induction in a gas flow, the composition of which corresponds to the composition of the gas flow during the cleaning of the crucible and the test sample. The oxygen system contained in the test sample is converted with carbon or the carbon system contained in the test sample is converted with oxygen to at least one oxidation product. If necessary, after oxidation to carbon dioxide, the oxidation product is preferably analyzed by infrared spectroscopy and the concentration of oxygen or carbon in the test sample is determined. Instead of infrared spectroscopy, another gas analysis method may be used, for example, a gas analysis method using a thermal conductivity detector (WLD).

坩堝材料的選擇係取決於要測定測試樣品中的氧含量還是碳含量。如果要測定測試樣品中的氧含量,則坩堝係由碳組成,在另一種情況下係由氧化物陶瓷(oxide ceramic)組成。在測定測試樣品中的氧含量的情況下,坩堝支架(holder)係由無氧材料(oxygen-free material)組成,較佳係由氮化硼嵌件(boron nitride insert)組成。如果使用碳坩堝,則在清潔坩堝與測試樣品期間以及在測定測試樣品本身中的氧含量期間,對包含測試樣品的坩堝進行感應加熱。The choice of crucible material depends on the determination of the oxygen content or carbon content of the test sample. If the oxygen content in the test sample is to be determined, the crucible is composed of carbon, and in another case is composed of oxide ceramic. In the case of measuring the oxygen content in the test sample, the crucible holder is composed of an oxygen-free material, preferably a boron nitride insert. If a carbon crucible is used, the crucible containing the test sample is induction heated during the cleaning of the crucible and the test sample and during the determination of the oxygen content in the test sample itself.

測試樣品係較佳由矽或含矽的半導體材料(例如矽鍺(silicon germanium))製成。半導體材料較佳是單晶或多晶的。半導體材料可摻雜有一或多種電活性摻雜劑(electrically active dopant)。The test sample is preferably made of silicon or a semiconductor material containing silicon (such as silicon germanium). The semiconductor material is preferably monocrystalline or polycrystalline. The semiconductor material may be doped with one or more electrically active dopants.

下面將參考附圖,使用較佳設計作為實例而更詳細地解釋本發明。The present invention will be explained in more detail below with reference to the drawings, using preferred designs as examples.

在測量裝置100中,測試樣品所在的坩堝1係佈置在坩堝支架3上的測量室2中。坩堝支架3係較佳由不含氧且不含碳的材料組成。坩堝支架3係較佳由氮化硼構成。測量室2係被設計成在包含氮氣的限定氣流中熔化坩堝1中所包含的測試樣品。In the measurement device 100, the crucible 1 where the test sample is located is arranged in the measurement chamber 2 on the crucible holder 3. The crucible holder 3 is preferably composed of a material containing no oxygen and no carbon. The crucible holder 3 is preferably composed of boron nitride. The measurement chamber 2 is designed to melt the test sample contained in the crucible 1 in a defined gas flow containing nitrogen.

為了提供通過測量室2的氣流,管線(line)4係連接到氣體供應(gas supply)5。In order to provide gas flow through the measurement chamber 2, a line 4 is connected to a gas supply 5.

測量裝置100包括感應加熱裝置(inductive heating device)6,該感應加熱裝置在測量室2中產生交變電磁場(alternating electromagnetic field),該電磁場係適當地與外部遮罩,坩堝1內的測試樣品可藉由該電磁場被加熱及熔化。The measurement device 100 includes an inductive heating device 6 which generates an alternating electromagnetic field in the measurement chamber 2 which is appropriately shielded from the external shield and the test sample in the crucible 1 can be The electromagnetic field is heated and melted.

首先,將坩堝1及包含在坩堝1中的測試樣品在氣流中清潔。在其過程中,測試樣品以及坩堝1(若需要)係被感應加熱。First, the crucible 1 and the test sample contained in the crucible 1 are cleaned in a gas flow. In the process, the test sample and crucible 1 (if required) are heated by induction.

如果需要,可提供鹵素燈7,借助於鹵素燈7可經由透明窗口8而將虛線繪製的光束照射到測試樣品,以便將測試樣品預熱到可進一步感應加熱測試樣品的溫度。If necessary, a halogen lamp 7 can be provided, by means of which the light beam drawn by the dotted line can be irradiated to the test sample via the transparent window 8 in order to preheat the test sample to a temperature that can further inductively heat the test sample.

在清潔坩堝與其中所包含的測試樣品之後,借助於感應加熱裝置6來熔化測試樣品,由此氧與碳反應而形成至少一種氧化產物。After cleaning the crucible and the test sample contained therein, the test sample is melted by means of the induction heating device 6, whereby oxygen and carbon react to form at least one oxidation product.

如果需要,在氧化成二氧化碳之後,該氧化產物係經由管線9而被送到檢測器部件(detector unit)10。在檢測器部件10中,來自管線9的氣體通過測量單元(measuring cell)11,該測量單元11被來自合適的光源(source)12(例如紅外光光源(infrared light source))的測量光束照射。在與測量單元11中的氣體相互作用之後,測量光束係照在檢測器13上,藉由該檢測器可在未顯示的評估裝置(evaluation device)中接收及評估檢測器信號。評估裝置係測定管線9的氣體中的至少一種氧化產物的含量,從而能夠測定測試樣品中的氧或碳的含量。If necessary, after oxidation to carbon dioxide, the oxidation product is sent to the detector unit 10 via line 9. In the detector part 10, the gas from the pipeline 9 passes through a measuring cell 11 which is irradiated by a measuring beam from a suitable source 12 (for example an infrared light source). After interacting with the gas in the measuring unit 11, the measuring beam is irradiated on the detector 13, by which the detector signal can be received and evaluated in an evaluation device (not shown). The evaluation device measures the content of at least one oxidation product in the gas of line 9 so that the content of oxygen or carbon in the test sample can be determined.

1:坩堝 2:測量室 3:坩堝支架 4:管線 5:氣體供應 6:感應加熱裝置 7:鹵素燈 8:窗口 9:管線 10:檢測器部件 11:測量單元 12:光源 13:檢測器 100:測量裝置1: crucible 2: Measurement room 3: Crucible bracket 4: pipeline 5: Gas supply 6: Induction heating device 7: Halogen lamp 8: window 9: pipeline 10: Detector parts 11: Measuring unit 12: Light source 13: Detector 100: measuring device

第1圖示意性地示出了測量裝置,其適用於實施根據本發明的方法。FIG. 1 schematically shows a measuring device, which is suitable for implementing the method according to the invention.

1:坩堝 1: crucible

2:測量室 2: Measurement room

3:坩堝支架 3: Crucible bracket

4:管線 4: pipeline

5:氣體供應 5: Gas supply

6:感應加熱裝置 6: Induction heating device

7:鹵素燈 7: Halogen lamp

8:窗口 8: window

9:管線 9: pipeline

10:檢測器部件 10: Detector parts

11:測量單元 11: Measuring unit

12:光源 12: Light source

13:檢測器 13: Detector

100:測量裝置 100: measuring device

Claims (2)

一種藉由氣體熔融分析(gas fusion analysis)來測定半導體材料中氧或碳含量的方法,包含: 在具有氮氣組成或氮氣與至少一種稀有氣體的混合物的氣流中感應加熱(inductively heating)坩堝中的半導體材料的測試樣品至不低於1300°C的溫度,從而清潔該坩堝與半導體材料的測試樣品;以及 在測量裝置(100)的測量室(2)中測定該測試樣品中的氧或碳含量,這包含在測量室(2)中在具有所述組成的氣流中感應加熱該測試樣品並在坩堝(1)中熔化該測試樣品; 使測試樣品中所含有的氧與碳反應或使測試樣品中所含有的碳與氧反應以形成至少一種氧化產物; 測定該至少一種氧化產物的量並使用該至少一種氧化產物的量作為測試樣品中所含氧或碳的含量的量度(measure)。A method for determining the content of oxygen or carbon in semiconductor materials by gas fusion analysis, including: Inductively heating the test sample of the semiconductor material in the crucible to a temperature of not less than 1300°C in a gas flow having a nitrogen composition or a mixture of nitrogen and at least one rare gas, thereby cleaning the test sample of the crucible and the semiconductor material ;as well as The oxygen or carbon content of the test sample is determined in the measurement chamber (2) of the measurement device (100). This involves inductively heating the test sample in the gas flow with the composition in the measurement chamber (2) and in the crucible ( 1) Melt the test sample; Reacting the oxygen contained in the test sample with carbon or reacting the carbon contained in the test sample with oxygen to form at least one oxidation product; The amount of the at least one oxidation product is determined and the amount of the at least one oxidation product is used as a measure of the content of oxygen or carbon contained in the test sample. 如請求項1所述的方法,更包含: 在該測量裝置(100)的測量室(2)中清潔該坩堝與測試樣品。The method according to claim 1, further comprising: Clean the crucible and test sample in the measurement chamber (2) of the measurement device (100).
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