WO2020052838A1 - 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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Publication number
WO2020052838A1
WO2020052838A1 PCT/EP2019/069666 EP2019069666W WO2020052838A1 WO 2020052838 A1 WO2020052838 A1 WO 2020052838A1 EP 2019069666 W EP2019069666 W EP 2019069666W WO 2020052838 A1 WO2020052838 A1 WO 2020052838A1
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Prior art keywords
measurement sample
carbon
oxygen
crucible
measurement
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PCT/EP2019/069666
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German (de)
French (fr)
Inventor
Dieter Rathmann
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Siltronic Ag
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Publication of WO2020052838A1 publication Critical patent/WO2020052838A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3563—Investigating 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus 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
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67242—Apparatus for monitoring, sorting or marking
    • H01L21/67253—Process monitoring, e.g. flow or thickness monitoring

Definitions

  • the invention relates to a method for determining oxygen or carbon in semiconductor material by means of gas fusion analysis (gas fusion analysis,
  • the GFA is a method that is used in particular to quantitatively determine oxygen or carbon in a measurement sample made of semiconductor material.
  • the measurement sample is melted, containing oxygen or
  • Analytical systems for determining oxygen or carbon in silicon for solar cells are available on the market (S. Sakakura, “Determination of Oxygen and Carbon of Silicon for Solar Cells”, Readout, English Edition No.14, pages 66-69, February 2011) .
  • the two elements are determined by means of GFA, whereby separate apparatuses with different measuring processes are required, which involve complex, multi-stage cleaning of the crucible and the measuring sample.
  • the cleaning of the measurement sample is intended to remove foreign material on the surface of the measurement sample, so that it is ensured that the subsequently determined
  • the object is achieved by a method for determining oxygen or carbon in semiconductor material by means of gas fusion analysis, comprising
  • Measurement sample is inductively heated in a gas stream with the same composition and melted in the crucible, and oxygen contained in the measurement sample with
  • Carbon or carbon contained in the measurement sample is reacted with oxygen to form at least one oxidation product, the amount of which is determined and used as a measure of the oxygen or carbon contained in the measurement sample.
  • the invention it is provided to clean the crucible and the measurement sample at the same time by inductively heating the measurement sample lying in the crucible and, if appropriate, the crucible itself to a temperature of at least 1300 ° C. in a gas stream consisting of nitrogen or a mixture of nitrogen and at least an inert gas, for example a mixture of nitrogen and argon.
  • a gas stream consisting of nitrogen or a mixture of nitrogen and at least an inert gas, for example a mixture of nitrogen and argon.
  • nitrogen impurities containing oxygen or carbon can be removed comparatively easily from the surface of the measurement sample, so that the measurement result is not falsified by foreign material adhering to the surface.
  • the presence of nitrogen causes nitriding of the semiconductor material, which causes the diffusion of
  • Semiconductor material that does not have sufficient intrinsic conductivity because it is not or only weakly doped it is preheated to a temperature of, for example, 300 ° C. to 500 ° C., for example by means of radiation from a halogen lamp.
  • the measurement sample is supplemented with semiconductor material which has sufficient intrinsic conductivity and whose content of oxygen and carbon is known and, according to Dilution in the volume of the measurement sample is low compared to the expected content of the measurement sample.
  • the known carbon content added by the supplement is preferably less than 10% of the expected carbon content of the measurement sample.
  • the specific electrical resistance of the semiconductor material added as a supplement is preferably not more than 0.5 ohmcm. Afterwards, such a measurement sample can also be easily inductively heated to the target cleaning temperature. If the crucible is made of carbon, none of this is required
  • the crucible is also inductively heated and, in the course of this, the measurement sample inside is preheated
  • the measurement sample is preferably heated to a temperature at which the measurement sample begins to melt on the surface.
  • the temperature of the measurement sample can be measured without contact, for example, using an IR thermometer.
  • the duration of the cleaning depends in particular on the weight of the measurement sample and the degree of contamination of the crucible and can be determined empirically, for example. For this purpose, measurement samples are cleaned over different periods of time and their surfaces are examined after cleaning.
  • the crucible and the measurement sample are cleaned outside the measuring device, in which the content of oxygen or carbon is determined.
  • they are transported into the measuring device under protective gas, for example argon.
  • protective gas for example argon.
  • Cleaning of the crucible and the measurement sample is carried out in the measuring device (in situ cleaning), in which the determination of the oxygen or carbon content in the measurement sample is carried out after the cleaning.
  • This has the advantage that the measurement sample no longer has to be cooled and transported before the determination of the oxygen content or the carbon content begins.
  • oxygen which adheres to the test sample as a foreign substance in a bound form, is reacted with carbon to form at least one oxidation product such as carbon monoxide.
  • This oxidation product is expediently analyzed, if appropriate after oxidation to carbon dioxide, by means of infrared spectrometry or another gas analysis method.
  • the concentration of oxygen on the surface of the measurement sample can be determined.
  • Measurement signal which indicates the presence of the oxidation product, has returned to this lower threshold after initially exceeding a predefined lower threshold.
  • the measurement sample is preferably no longer cooled before its oxygen content or its carbon content is determined.
  • the measurement sample lying in the crucible is inductively heated and melted in a gas stream, the composition of which corresponds to that of the gas stream during the cleaning of the crucible and the measurement sample.
  • Oxygen contained in the measurement sample is reacted with carbon or carbon contained in the interior of the measurement sample is reacted with at least one oxidation product.
  • Oxidation product optionally after oxidation to carbon dioxide, is preferably analyzed by means of infrared spectrometry and the concentration of oxygen or carbon in the measurement sample is determined.
  • Another gas analysis method can be used in infrared spectrometry, for example a gas analysis method in which a WLD detector (thermal conductivity detector) is used.
  • WLD detector thermo conductivity detector
  • the choice of the material of the crucible depends on whether it is intended to determine the oxygen content or the carbon content in the measurement sample. If the oxygen content of the measurement sample is intended to be determined, the crucible consists of carbon, in the other case of oxidic ceramic. In the case of determining the oxygen content, the crucible holder consists of oxygen-free material, preferably an insert made of boron nitride. In the case of using a crucible made of carbon, the crucible is cleaned during the cleaning of the crucible and the measurement sample and heated inductively during the determination of the oxygen content in the measurement sample itself.
  • the measurement sample preferably consists of silicon or a semiconductor material which contains silicon, for example silicon germanium.
  • the semiconductor material is preferably single crystal or polycrystalline.
  • the semiconductor material can be doped with one or more electrically active dopants.
  • FIG. 1 schematically shows a measuring device which is suitable for carrying out the method according to the invention.
  • a crucible 1 in which a measurement sample lies, is arranged in a measuring chamber 2 on a crucible holder 3.
  • the crucible holder 3 is preferably made of a material whose structure is free of oxygen and free of carbon.
  • the crucible holder 3 preferably consists of boron nitride.
  • Measuring chamber 2 is designed to melt the measurement sample in a defined gas flow, which contains nitrogen, in the crucible 1.
  • a line 4 is provided which is connected to a gas supply 5.
  • the measuring device 100 comprises an inductive heating device 6, which in the
  • Measuring chamber 2 which is suitably shielded from the outside
  • alternating electromagnetic field is generated, by means of which the measurement sample in the crucible 1 can be heated and melted.
  • the crucible 1 and the measurement sample lying therein are cleaned in the gas stream.
  • the measurement sample and optionally the crucible 1 are heated inductively.
  • a halogen lamp 7 can be provided, by means of which a light beam illustrated in dashed lines can be irradiated through a transparent window 8 to the measurement sample in order to be able to preheat the measurement sample to a temperature which enables the measurement sample to be heated further inductively.
  • the measurement sample After cleaning the crucible and the measurement sample contained therein, the measurement sample is melted by means of the inductive heating device 6, oxygen and carbon reacting to form at least one oxidation product.
  • This oxidation product is passed via a line 9 to a detector unit 10.
  • the gas of the line 9 is passed through a measuring cell 11, which is irradiated by a measuring beam from a suitable source 12, for example an infrared light source.
  • a suitable source 12 for example an infrared light source.
  • the measuring beam strikes a detector 13 in the measuring cell 11, by means of which a detector signal can be obtained and evaluated in an evaluation device (not shown).
  • the Evaluation device determines a content of the at least one oxidation product in the gas of line 9 and in this way allows the determination of the
  • Oxygen content or carbon content in the measurement sample is Oxygen content or carbon content in the measurement sample.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

The invention relates to a method for determining oxygen or carbon in semiconductor material by means of gas fusion analysis, comprising: cleaning a crucible and a measurement sample by inductively heating the measurement sample present in the crucible to a temperature of not less than 1300 °C in a gas stream of nitrogen or a mixture of nitrogen and at least one inert gas; and determining the oxygen content or the carbon content in the measurement sample of semiconductor material in a measurement chamber (2) of a measurement device (100) in which the measurement sample is inductively heated in a gas stream having the same composition and melted in the crucible (1); and oxygen contained in the measurement sample is reacted with carbon or carbon contained in the measurement sample is reacted with oxygen to form at least one oxidation product, the amount of which is determined by and is used as a measurement of the oxygen or carbon contained in the measurement sample.

Description

Verfahren zur Bestimmung von Sauerstoff oder Kohlenstoff in Halbleitermaterial  Method for the determination of oxygen or carbon in semiconductor material
Gegenstand der Erfindung ist ein Verfahren zur Bestimmung von Sauerstoff oder Kohlenstoff in Halbleitermaterial mittels Gasfusionsanalyse (gas fusion analysis,The invention relates to a method for determining oxygen or carbon in semiconductor material by means of gas fusion analysis (gas fusion analysis,
GFA). GFA).
Die GFA ist eine Methode, die insbesondere verwendet wird, um Sauerstoff oder Kohlenstoff in einer Messprobe aus Halbleitermaterial quantitativ zu bestimmen. The GFA is a method that is used in particular to quantitatively determine oxygen or carbon in a measurement sample made of semiconductor material.
Hierzu wird die Messprobe geschmolzen, darin enthaltener Sauerstoff oder For this purpose, the measurement sample is melted, containing oxygen or
Kohlenstoff in eine Verbindung überführt, und deren Menge spektroskopisch bestimmt. Carbon converted into a compound, and the amount determined spectroscopically.
Stand der Technik / Probleme State of the art / problems
Analysensysteme zum Bestimmen von Sauerstoff oder Kohlenstoff in Silizium für Solarzellen sind auf dem Markt verfügbar (S. Sakakura,„Determination of Oxygen and Carbon of Silicon for Solar Cells“, Readout, English Edition No.14, pages 66-69, February 2011 ). Die beiden Elemente werden mittels GFA bestimmt, wobei getrennte Apparaturen mit verschiedenen Messvorgängen erforderlich sind, die eine aufwändige mehrstufige Reinigung des Tiegels und der Messprobe umfassen. Mit der Reinigung der Messprobe wird beabsichtigt, Fremdmaterial auf der Oberfläche der Messprobe zu beseitigen, damit sichergestellt ist, dass der im Anschluss bestimmte Analytical systems for determining oxygen or carbon in silicon for solar cells are available on the market (S. Sakakura, “Determination of Oxygen and Carbon of Silicon for Solar Cells”, Readout, English Edition No.14, pages 66-69, February 2011) . The two elements are determined by means of GFA, whereby separate apparatuses with different measuring processes are required, which involve complex, multi-stage cleaning of the crucible and the measuring sample. The cleaning of the measurement sample is intended to remove foreign material on the surface of the measurement sample, so that it is ensured that the subsequently determined
Sauerstoffgehalt oder Kohlenstoffgehalt dem Inneren (bulk) der Messprobe Oxygen content or carbon content of the inside (bulk) of the measurement sample
zugeordnet werden kann. can be assigned.
DE 10 2014 217 514 A1 beschreibt ein Verfahren zur Bestimmung des Kohlenstoffs in einer Messprobe aus Halbleitermaterial, das auf Gasfusionsanalyse basiert. Es ist wünschenswert, die Bestimmung von Sauerstoff oder Kohlenstoff in DE 10 2014 217 514 A1 describes a method for determining the carbon in a measurement sample made of semiconductor material, which is based on gas fusion analysis. It is desirable to determine oxygen or carbon in
Halbleitermaterial mittels Gasfusionsanalyse zu verbessern. Die Aufgabe wird gelöst durch ein Verfahren zur Bestimmung von Sauerstoff oder Kohlenstoff in Halbleitermaterial mittels Gasfusionsanalyse, umfassend To improve semiconductor material by means of gas fusion analysis. The object is achieved by a method for determining oxygen or carbon in semiconductor material by means of gas fusion analysis, comprising
das Reinigen eines Tiegels und einer Messprobe durch induktives Erhitzen der im Tiegel liegenden Messprobe auf eine Temperatur von nicht weniger als 1300 °C in einem Gasstrom aus Stickstoff oder einer Mischung aus Stickstoff und mindestens einem Edelgas und the cleaning of a crucible and a measurement sample by induction heating of the measurement sample lying in the crucible to a temperature of not less than 1300 ° C. in a gas stream of nitrogen or a mixture of nitrogen and at least one noble gas and
das Bestimmen des Sauerstoffgehalts oder des Kohlenstoffgehalts in der Messprobe aus Halbleitermaterial in einer Messkammer einer Messvorrichtung, wo die determining the oxygen content or the carbon content in the measurement sample of semiconductor material in a measurement chamber of a measuring device, where the
Messprobe in einem Gasstrom mit gleicher Zusammensetzung induktiv erhitzt und im Tiegel geschmolzen wird, und in der Messprobe enthaltener Sauerstoff mit Measurement sample is inductively heated in a gas stream with the same composition and melted in the crucible, and oxygen contained in the measurement sample with
Kohlenstoff oder in der Messprobe enthaltener Kohlenstoff mit Sauerstoff zu mindestens einem Oxidationsprodukt umgesetzt wird, dessen Menge bestimmt und als ein Maß für den in der Messprobe enthaltenen Sauerstoff oder Kohlenstoff verwendet wird. Carbon or carbon contained in the measurement sample is reacted with oxygen to form at least one oxidation product, the amount of which is determined and used as a measure of the oxygen or carbon contained in the measurement sample.
Erfindungsgemäß ist vorgesehen, den Tiegel und die Messprobe gleichzeitig zu reinigen und zwar durch induktives Erhitzen der im Tiegel liegenden Messprobe und gegebenenfalls des Tiegels selbst auf eine Temperatur von mindestens 1300 °C in einem Gasstrom, der aus Stickstoff oder aus einer Mischung von Stickstoff und mindestens einem Edelgas besteht, beispielsweise einer Mischung aus Stickstoff und Argon. In Gegenwart von Stickstoff lassen sich Sauerstoff oder Kohlenstoff enthaltende Verunreinigungen von der Oberfläche der Messprobe vergleichsweise einfach entfernen, so dass das Messergebnis durch an der Oberfläche anhaftendes Fremdmaterial nicht verfälscht wird. Darüber hinaus bewirkt die Gegenwart von Stickstoff eine Nitridierung des Halbleitermaterials, was die Diffusion von According to the invention, it is provided to clean the crucible and the measurement sample at the same time by inductively heating the measurement sample lying in the crucible and, if appropriate, the crucible itself to a temperature of at least 1300 ° C. in a gas stream consisting of nitrogen or a mixture of nitrogen and at least an inert gas, for example a mixture of nitrogen and argon. In the presence of nitrogen, impurities containing oxygen or carbon can be removed comparatively easily from the surface of the measurement sample, so that the measurement result is not falsified by foreign material adhering to the surface. In addition, the presence of nitrogen causes nitriding of the semiconductor material, which causes the diffusion of
Fremdmaterial aus dem Inneren der Messprobe zu deren Oberfläche erleichtert.  Foreign material from the inside of the measurement sample to its surface is easier.
Besteht die Messprobe, die zum Reinigen induktiv erhitzt werden soll, aus Is the measurement sample that is to be heated inductively for cleaning
Halbleitermaterial, das keine ausreichende Eigenleitfähigkeit besitzt, weil es nicht oder nur schwach dotiert ist, wird es auf eine Temperatur von beispielsweise 300 °C bis 500 °C vorerhitzt, beispielsweise mittels Strahlung einer Halogenlampe. Oder die Messprobe wird mit Halbleitermaterial ergänzt, das ausreichende Eigenleitfähigkeit besitzt und dessen Gehalt an Sauerstoff und Kohlenstoff bekannt und, nach Verdünnung in das Volumen der Messprobe, niedrig im Vergleich zum erwarteten Gehalt der Messprobe ist. Vorzugsweise ist der durch die Ergänzung addierte bekannte Kohlenstoffgehalt kleiner als 10% des erwarteten Kohlenstoffgehalts der Messprobe. Der spezifische elektrische Widerstand des zur Ergänzung hinzugefügten Halbleitermaterials beträgt vorzugsweise nicht mehr als 0,5 Ohmcm. Danach kann auch eine solche Messprobe problemlos auf die Zieltemperatur der Reinigung induktiv erhitzt werden. Besteht der Tiegel aus Kohlenstoff, bedarf es keiner dieser Semiconductor material that does not have sufficient intrinsic conductivity because it is not or only weakly doped, it is preheated to a temperature of, for example, 300 ° C. to 500 ° C., for example by means of radiation from a halogen lamp. Or the measurement sample is supplemented with semiconductor material which has sufficient intrinsic conductivity and whose content of oxygen and carbon is known and, according to Dilution in the volume of the measurement sample is low compared to the expected content of the measurement sample. The known carbon content added by the supplement is preferably less than 10% of the expected carbon content of the measurement sample. The specific electrical resistance of the semiconductor material added as a supplement is preferably not more than 0.5 ohmcm. Afterwards, such a measurement sample can also be easily inductively heated to the target cleaning temperature. If the crucible is made of carbon, none of this is required
besonderen Vorkehrungen. In diesem Fall wird auch der Tiegel induktiv erhitzt und im Zuge dessen auch die darin liegende Messprobe vorerhitzt special arrangements. In this case, the crucible is also inductively heated and, in the course of this, the measurement sample inside is preheated
Vorzugsweise wird die Messprobe im Verlauf der Reinigung auf eine Temperatur erhitzt, bei der die Messprobe oberflächlich zu schmelzen beginnt. Die Temperatur der Messprobe kann beispielsweise mittels eines IR-Thermometers kontaktlos gemessen werden. Die Dauer der Reinigung hängt insbesondere vom Gewicht der Messprobe und dem Verunreinigungsgrad des Tiegels ab und kann beispielsweise empirisch bestimmt werden. Hierzu werden Messproben über unterschiedliche Zeiträume gereinigt und deren Oberflächen nach der Reinigung begutachtet. In the course of cleaning, the measurement sample is preferably heated to a temperature at which the measurement sample begins to melt on the surface. The temperature of the measurement sample can be measured without contact, for example, using an IR thermometer. The duration of the cleaning depends in particular on the weight of the measurement sample and the degree of contamination of the crucible and can be determined empirically, for example. For this purpose, measurement samples are cleaned over different periods of time and their surfaces are examined after cleaning.
Gemäß einer Ausgestaltungsform der Erfindung erfolgt die Reinigung des Tiegels und der Messprobe außerhalb der Messvorrichtung, in der der Gehalt an Sauerstoff oder Kohlenstoff bestimmt wird. In diesem Fall werden im Anschluss an die Reinigung der Tiegel mit der darin liegenden Messprobe unter Schutzgas, beispielsweise Argon, in die Messvorrichtung transportiert. Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung wird die According to one embodiment of the invention, the crucible and the measurement sample are cleaned outside the measuring device, in which the content of oxygen or carbon is determined. In this case, following the cleaning of the crucibles with the measurement sample lying therein, they are transported into the measuring device under protective gas, for example argon. According to a further preferred embodiment of the invention, the
Reinigung des Tiegels und der Messprobe in der Messvorrichtung durchgeführt (in situ Reinigung), in der im Anschluss an die Reinigung die Bestimmung des Gehalts an Sauerstoff oder Kohlenstoff in der Messprobe vorgenommen wird. Das hat den Vorteil, dass die Messprobe nicht mehr abgekühlt und transportiert werden muss, bevor mit der Bestimmung des Sauerstoffgehalts oder des Kohlenstoffgehalts begonnen wird. Im Zuge der in situ Reinigung wird Sauerstoff, der in gebundener Form als Fremdstoff auf der Messprobe haftet, mit Kohlenstoff zu mindestens einem Oxidationsprodukt wie Kohlenmonoxid umgesetzt. Dieses Oxidationsprodukt wird zweckmäßigerweise, gegebenenfalls nach einer Oxidation zu Kohlendioxid, mittels Infrarotspektrometrie oder einer anderen Gasanalysenmethode analysiert. Im Zuge dessen kann die Konzentration von Sauerstoff auf der Oberfläche der Messprobe bestimmt werden.Cleaning of the crucible and the measurement sample is carried out in the measuring device (in situ cleaning), in which the determination of the oxygen or carbon content in the measurement sample is carried out after the cleaning. This has the advantage that the measurement sample no longer has to be cooled and transported before the determination of the oxygen content or the carbon content begins. In the course of in-situ cleaning, oxygen, which adheres to the test sample as a foreign substance in a bound form, is reacted with carbon to form at least one oxidation product such as carbon monoxide. This oxidation product is expediently analyzed, if appropriate after oxidation to carbon dioxide, by means of infrared spectrometry or another gas analysis method. In the course of this, the concentration of oxygen on the surface of the measurement sample can be determined.
Die in situ Reinigung wird als vollzogen betrachtet, wenn die Intensität des In situ cleaning is considered to have been accomplished when the intensity of the
Messsignals, das das Vorhandensein des Oxidationsprodukts anzeigt, nach anfänglichem Überschreiten einer vordefinierten unteren Schwelle zu dieser unteren Schwelle zurückgekehrt ist. Die Messprobe wird vorzugsweise nicht mehr abgekühlt, bevor deren Sauerstoffgehalt oder deren Kohlenstoffgehalt bestimmt wird. Measurement signal, which indicates the presence of the oxidation product, has returned to this lower threshold after initially exceeding a predefined lower threshold. The measurement sample is preferably no longer cooled before its oxygen content or its carbon content is determined.
Zum Bestimmen des Sauerstoffgehalts oder des Kohlenstoffgehalts wird die im Tiegel liegende Messprobe in einem Gasstrom, dessen Zusammensetzung derjenigen des Gasstroms während des Reinigens des Tiegels und der Messprobe entspricht, induktiv erhitzt und geschmolzen. Im Inneren der Messprobe enthaltener Sauerstoff wird mit Kohlenstoff oder im Inneren der Messprobe enthaltener Kohlenstoff mit Sauerstoff zu mindestens einem Oxidationsprodukt umgesetzt. Dieses To determine the oxygen content or the carbon content, the measurement sample lying in the crucible is inductively heated and melted in a gas stream, the composition of which corresponds to that of the gas stream during the cleaning of the crucible and the measurement sample. Oxygen contained in the measurement sample is reacted with carbon or carbon contained in the interior of the measurement sample is reacted with at least one oxidation product. This
Oxidationsprodukt wird, gegebenenfalls nach einer Oxidation zu Kohlendioxid, vorzugsweise mittels Infrarotspektrometrie analysiert und die Konzentration von Sauerstoff oder Kohlenstoff in der Messprobe bestimmt. An Stelle von Oxidation product, optionally after oxidation to carbon dioxide, is preferably analyzed by means of infrared spectrometry and the concentration of oxygen or carbon in the measurement sample is determined. Instead of
Infrarotspektrometrie kann ein anderes Gasanalyseverfahren verwendet werden, beispielsweise ein Gasanalyseverfahren, bei dem ein WLD-Detektor (thermal conductivity detector) eingesetzt wird. Another gas analysis method can be used in infrared spectrometry, for example a gas analysis method in which a WLD detector (thermal conductivity detector) is used.
Die Wahl des Materials des Tiegels hängt davon ab, ob in der Messprobe der Gehalt an Sauerstoff oder der Gehalt an Kohlenstoff zu bestimmen beabsichtigt ist. Falls der Sauerstoffgehalt der Messprobe zu bestimmen beabsichtigt ist, besteht der Tiegel aus Kohlenstoff, im anderen Fall aus oxidischer Keramik. Im Fall der Bestimmung des Sauerstoffgehalts besteht die Tiegelhalterung aus Sauerstoff-freiem Material, bevorzugt aus einem Einsatz aus Bornitrid. Im Fall der Verwendung eines Tiegels aus Kohlenstoff wird der Tiegel während der Reinigung des Tiegels und der Messprobe und während der Bestimmung des Sauerstoffgehalts in der Messprobe selbst induktiv erhitzt. The choice of the material of the crucible depends on whether it is intended to determine the oxygen content or the carbon content in the measurement sample. If the oxygen content of the measurement sample is intended to be determined, the crucible consists of carbon, in the other case of oxidic ceramic. In the case of determining the oxygen content, the crucible holder consists of oxygen-free material, preferably an insert made of boron nitride. In the case of using a crucible made of carbon, the crucible is cleaned during the cleaning of the crucible and the measurement sample and heated inductively during the determination of the oxygen content in the measurement sample itself.
Die Messprobe besteht vorzugsweise aus Silizium oder aus einem Halbleitermaterial, das Silizium enthält, beispielsweise aus Siliziumgermanium. Das Halbleitermaterial ist vorzugsweise einkristallin oder polykristallin. Das Halbleitermaterial kann mit einem oder mehreren elektrisch aktiven Dotierstoffen dotiert sein. The measurement sample preferably consists of silicon or a semiconductor material which contains silicon, for example silicon germanium. The semiconductor material is preferably single crystal or polycrystalline. The semiconductor material can be doped with one or more electrically active dopants.
Die Erfindung wird nachfolgend unter Bezugnahme auf die beigefügte Zeichnung am Beispiel der bevorzugten Ausführungsform näher erläutert. The invention is explained in more detail below with reference to the accompanying drawing using the example of the preferred embodiment.
Kurze Beschreibung der Zeichnung Brief description of the drawing
In Figur 1 ist eine Messvorrichtung, die zur Durchführung des erfindungsgemäßen Verfahrens geeignet ist, schematisch dargestellt. FIG. 1 schematically shows a measuring device which is suitable for carrying out the method according to the invention.
Liste der verwendeten Bezugszeichen List of the reference symbols used
100 Messvorrichtung 100 measuring device
1 Tiegel 1 crucible
2 Messkammer  2 measuring chamber
3 Tiegelhalterung  3 crucible holder
4 Leitung  4 line
5 Gasversorgung  5 gas supply
6 induktive Heizeinrichtung 6 inductive heating device
7 Halogenlampe  7 halogen lamp
8 Fenster  8 windows
9 Leitung  9 line
10 Detektoreinheit  10 detector unit
11 Messzelle 11 measuring cell
12 Quelle  12 source
13 Detektor In der Messvorrichtung 100 ist ein Tiegel 1 , in dem eine Messprobe liegt, in einer Messkammer 2 auf einer Tiegelhalterung 3 angeordnet. Die Tiegelhalterung 3 besteht vorzugsweise aus einem Material, dessen Struktur frei von Sauerstoff und frei von Kohlenstoff ist. Vorzugsweise besteht die Tiegelhalterung 3 aus Bornitrid. Die 13 detector In the measuring device 100, a crucible 1, in which a measurement sample lies, is arranged in a measuring chamber 2 on a crucible holder 3. The crucible holder 3 is preferably made of a material whose structure is free of oxygen and free of carbon. The crucible holder 3 preferably consists of boron nitride. The
Messkammer 2 ist dazu ausgebildet, die Messprobe in einem definierten Gasstrom, der Stickstoff enthält, im Tiegel 1 zu schmelzen. Measuring chamber 2 is designed to melt the measurement sample in a defined gas flow, which contains nitrogen, in the crucible 1.
Zur Bereitstellung des Gasstroms durch die Messkammer 2 ist eine Leitung 4 vorgesehen, die an eine Gasversorgung 5 angeschlossen ist. To provide the gas flow through the measuring chamber 2, a line 4 is provided which is connected to a gas supply 5.
Die Messvorrichtung 100 umfasst eine induktive Heizeinrichtung 6, die in der The measuring device 100 comprises an inductive heating device 6, which in the
Messkammer 2, die nach außen in geeigneter Weise abgeschirmt ist, ein Measuring chamber 2, which is suitably shielded from the outside
elektromagnetisches Wechselfeld erzeugt, durch welches die Messprobe im Tiegel 1 erhitzt und geschmolzen werden kann. alternating electromagnetic field is generated, by means of which the measurement sample in the crucible 1 can be heated and melted.
Zunächst werden der Tiegel 1 und die darin liegende Messprobe im Gasstrom gereinigt. Im Zuge dessen werden die Messprobe und gegebenenfalls der Tiegel 1 induktiv erhitzt. First, the crucible 1 and the measurement sample lying therein are cleaned in the gas stream. In the course of this, the measurement sample and optionally the crucible 1 are heated inductively.
Gegebenenfalls kann eine Halogenlampe 7 vorgesehen sein, mittels derer ein gestrichelt veranschaulichter Lichtstrahl durch ein transparentes Fenster 8 zur Messprobe eingestrahlt werden kann, um die Messprobe auf eine Temperatur vorerhitzen zu können, die das induktive Weitererhitzen der Messprobe ermöglicht. Optionally, a halogen lamp 7 can be provided, by means of which a light beam illustrated in dashed lines can be irradiated through a transparent window 8 to the measurement sample in order to be able to preheat the measurement sample to a temperature which enables the measurement sample to be heated further inductively.
Nach dem Reinigen des Tiegels und der darin enthaltenen Messprobe wird die Messprobe mittels der induktiven Heizeinrichtung 6 geschmolzen, wobei Sauerstoff und Kohlenstoff zu mindestens einem Oxidationsprodukt reagieren. After cleaning the crucible and the measurement sample contained therein, the measurement sample is melted by means of the inductive heating device 6, oxygen and carbon reacting to form at least one oxidation product.
Dieses Oxidationsprodukt wird, gegebenenfalls nach einer Oxidation zu Kohlendioxid, über eine Leitung 9 zu einer Detektoreinheit 10 geleitet. In der Detektoreinheit 10 wird das Gas der Leitung 9 durch eine Messzelle 11 geführt, die von einem Messstrahl einer geeigneten Quelle 12, beispielsweise einer Infrarotlichtquelle, durchstrahlt wird. Der Messstrahl trifft nach der Interaktion mit dem Gas in der Messzelle 11 auf einen Detektor 13 auf, mittels dessen ein Detektorsignal erhalten und in einer nicht dargestellten Auswerteeinrichtung ausgewertet werden kann. Die Auswerteeinrichtung ermittelt einen Gehalt des mindestens einen Oxidationsprodukts im Gas der Leitung 9 und erlaubt auf diese Weise die Bestimmung des This oxidation product, optionally after oxidation to carbon dioxide, is passed via a line 9 to a detector unit 10. In the detector unit 10, the gas of the line 9 is passed through a measuring cell 11, which is irradiated by a measuring beam from a suitable source 12, for example an infrared light source. After the interaction with the gas, the measuring beam strikes a detector 13 in the measuring cell 11, by means of which a detector signal can be obtained and evaluated in an evaluation device (not shown). The Evaluation device determines a content of the at least one oxidation product in the gas of line 9 and in this way allows the determination of the
Sauerstoffgehalts oder des Kohlenstoffgehalts in der Messprobe. Oxygen content or carbon content in the measurement sample.

Claims

Patentansprüche Claims
1. Verfahren zur Bestimmung von Sauerstoff oder Kohlenstoff in Halbleitermaterial mittels Gasfusionsanalyse, umfassend 1. A method for determining oxygen or carbon in semiconductor material by means of gas fusion analysis, comprising
das Reinigen eines Tiegels und einer Messprobe durch induktives Erhitzen der im Tiegel liegenden Messprobe auf eine Temperatur von nicht weniger als 1300 °C in einem Gasstrom aus Stickstoff oder einer Mischung aus Stickstoff und mindestens einem Edelgas und the cleaning of a crucible and a measurement sample by induction heating of the measurement sample lying in the crucible to a temperature of not less than 1300 ° C. in a gas stream of nitrogen or a mixture of nitrogen and at least one noble gas and
das Bestimmen des Sauerstoffgehalts oder des Kohlenstoffgehalts in der Messprobe aus Halbleitermaterial in einer Messkammer (2) einer Messvorrichtung (100), wo die Messprobe in einem Gasstrom mit gleicher Zusammensetzung induktiv erhitzt und im Tiegel (1 ) geschmolzen wird, und in der Messprobe enthaltener Sauerstoff mit Kohlenstoff oder in der Messprobe enthaltener Kohlenstoff mit Sauerstoff zu mindestens einem Oxidationsprodukt umgesetzt wird, dessen Menge bestimmt und als ein Maß für den in der Messprobe enthaltenen Sauerstoff oder Kohlenstoff verwendet wird. determining the oxygen content or the carbon content in the measurement sample made of semiconductor material in a measurement chamber (2) of a measurement device (100), where the measurement sample is inductively heated in a gas stream with the same composition and melted in the crucible (1), and oxygen contained in the measurement sample with carbon or carbon contained in the measurement sample is reacted with oxygen to form at least one oxidation product, the amount of which is determined and used as a measure of the oxygen or carbon contained in the measurement sample.
2. Verfahren nach Anspruch 1 , weiterhin umfassend 2. The method of claim 1, further comprising
das Reinigen des Tiegels und der Messprobe in der Messkammer (2) der cleaning the crucible and the test sample in the measuring chamber (2)
Messvorrichtung (100). Measuring device (100).
PCT/EP2019/069666 2018-09-12 2019-07-22 Method for determining oxygen or carbon in semiconductor material WO2020052838A1 (en)

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