WO2004030068A1 - Method for the production of an electronic component comprising a praseodymium oxide layer - Google Patents

Method for the production of an electronic component comprising a praseodymium oxide layer Download PDF

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Publication number
WO2004030068A1
WO2004030068A1 PCT/EP2003/010413 EP0310413W WO2004030068A1 WO 2004030068 A1 WO2004030068 A1 WO 2004030068A1 EP 0310413 W EP0310413 W EP 0310413W WO 2004030068 A1 WO2004030068 A1 WO 2004030068A1
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WIPO (PCT)
Prior art keywords
praseodymium oxide
silicon
substrate surface
acidic solution
substrate
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PCT/EP2003/010413
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German (de)
French (fr)
Inventor
Udo Schwalke
Hans-Joachim MÜSSIG
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Ihp Gmbh - Innovations For High Performance Microelectronics / Institut Für Innovative Mikroelektronik
Technische Universität Darmstadt
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Publication of WO2004030068A1 publication Critical patent/WO2004030068A1/en

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    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • H01L21/32137—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas of silicon-containing layers

Definitions

  • the invention relates to a method for the selective removal of material containing praseodymium oxide from a silicon-containing substrate surface.
  • the invention further relates to a method for removing light-sensitive lacquer from a substrate surface containing praseodymium oxide.
  • the invention relates to a method for the selective anisotropic removal of at least part of a silicon layer from a silicon-containing substrate with an intermediate layer arranged between the substrate and the silicon layer and containing praseodymium oxide.
  • praseodymium oxide for example in the form of Pr 2 O 3
  • Praseodymium oxide has a dielectric constant k of about 30 and therefore allows a layer thickness increased by a factor of 30 / 3.9 compared to an equivalent SiO 2 layer. This means that tunnel currents can be suppressed.
  • Another problem area is the removal of light-sensitive paints as part of the lithographic structure formation in the manufacture of components.
  • the varnishes must be removed after an etching step or an implantation step.
  • Common wet chemical paint removal methods work with acids that dissolve praseodymium oxide.
  • Specify paint removal that does not impair a praseodymium oxide layer arranged under the paint.
  • a step of anisotropic reactive ion etching (RIE) of silicon-containing material has to be carried out, for example when forming the so-called poly-silicon gate of a MOSFET, which is formed from polycrystalline silicon.
  • RIE anisotropic reactive ion etching
  • the object of the invention is to solve the technical problems mentioned, which occur in particular when integrating praseodymium oxide into CMOS processes.
  • the problem of a wet chemical process is solved by a method for the selective removal of material containing praseodymium oxide from a silicon-containing substrate surface, in which the material containing praseodymium oxide is brought into contact with an acidic solution.
  • the invention is based on the knowledge that acidic solutions are suitable for selectively removing praseodymium oxide layers from silicon-containing substrate surfaces.
  • an acidic solution containing hydrochloric acid is the solution known from the RCA cleaning process. It contains a 6: 1: 1 solution of H 2 O: H 2 O 2 : HCl.
  • Another suitable acidic solution contains phosphoric acid (H 3 PO 4 ). It is important that the acidic solution according to the invention does not attack silicon.
  • a particularly preferred embodiment of the invention is a method in which the acidic solution contains hydrochloric acid with a weight fraction between 0.6% and 0.9%.
  • the best results regarding the etching speed were achieved with an acidic solution containing hydrochloric acid with a weight fraction between 0.7% and 0.8%.
  • An acidic solution with hydrochloric acid with a weight fraction of 0.75% which currently appears to be the most suitable for process integration, has a rate of 28 nm / min. Because of the high, but technically controllable etching rate, this embodiment of the method according to the invention is particularly well suited to selectively removing praseodymium oxide layers from silicon-containing surfaces.
  • the method according to the invention is preferably used where the substrate surface predominantly contains silicon or even consists entirely of silicon. However, it is also suitable for silicon-containing alloys, such as silicon germanium. Substrate surfaces which contain carbon-doped silicon or silicon germanium in whole or in sections can also be treated with the method according to the invention.
  • the material to be selectively removed predominantly contains praseodymium oxide or consists entirely of praseodymium oxide.
  • Materials which have one or more other constituents besides praseodymium oxide can also be selectively removed with the method according to the invention, since at least the praseodymium oxide constituents are etched by contact with the acidic solution. As a result, the material is so structurally attacked that it is removed from the silicon-containing substrate surface.
  • the method according to the invention can be carried out in different variants. Both dip etching, in which the substrate surface with the material containing praseodymium oxide is at least partially immersed in the acidic solution, and spray etching, in which the substrate surface is sprayed with the material containing praseodymium oxide with the acidic solution, are conceivable.
  • the problem of lacquer removal is solved by a method for removing light-sensitive lacquer from a substrate surface containing praseodymium oxide, in which the light-sensitive lacquer is brought into contact with an organic solvent.
  • the invention is based on the finding that only organic solvents are suitable for removing the lacquer without impairing the praseodymium oxide layer.
  • an acetone-containing solvent is used as a suitable solvent.
  • pure acetone can also be used.
  • an organic solvent is used, which is sold under the name AZ100 by the Clariant company (http://www.clariant.com). This can also be used neat or in a mixture with another organic solvent.
  • the lacquer is removed by methods which are otherwise known per se in process engineering.
  • an immersion process is preferably used to remove the paint.
  • At least the substrate surface with the lacquer or the entire substrate is immersed in the organic solvent. Praseodymium oxide or layers containing silicon underneath the lacquer layer are not attacked
  • an oxygen plasma can also be used to etch the paint.
  • the oxygen radicals present in the plasma have a negative influence on the praseodymium oxide / silicon (001) interface. Therefore, the use of an oxygen plasma is not preferred.
  • the problem of developing a selective RIE process by a method for selectively anisotropically removing at least part of a silicon-containing layer from a silicon-containing substrate with a layer between the substrate and the silicon Intermediate layer arranged zium layer and containing praseodymium oxide, in which a plasma formed from a reaction gas under electrical alternating voltage comes into contact with the substrate in a reaction chamber, characterized in that the reaction gas contains SF 6 CI 2 .
  • the method according to the invention avoids damage to the silicon substrate. It is particularly suitable for etching a polysilicon gate structure.
  • the selectivity of the etching process is 300 times greater than that of praseodymium oxide compared to the polysilicon gate.
  • the method according to the invention is also suitable for etching silicon-containing alloys.

Abstract

The invention relates to the process technological integration of praseodymium oxide into CMOS processes as a dielectric so as to produce electronic components having a particularly high scale of integration. According to an inventive method for selectively removing material containing praseodymium oxide from a silicon-containing substrate surface, the material containing praseodymium oxide is brought into contact with an acidic solution. According to an inventive method for removing light-sensitive lacquer from a substrate surface containing praseodymium oxide, the light-sensitive lacquer is brought into contact with an organic solvent. In an inventive method for the selective anisotropic removal of at least one portion of a layer containing silicon from a silicon-containing substrate which comprises an intermediate layer that is disposed between the substrate and the silicon layer and contains praseodymium oxide, a plasma formed from a reaction gas by applying an alternating current is contacted with the substrate in a reaction chamber, the reaction gas containing SF6/Cl2.

Description

Verfahren zur Herstellung eines elektronischen Bauelements mit einer Praseodymoxid-Schicht Method for producing an electronic component with a praseodymium oxide layer
Die Erfindung betrifft ein Verfahren zum selektiven Entfernen von Praseodymoxid enthaltendem Material von einer siliziumhaltigen Substratoberfläche. Die Erfindung betrifft weiterhin ein Verfahren zum Entfernen von lichtempfindlichem Lack von einer Praseodymoxid enthaltenden Substratoberfläche. Schließlich betrifft die Erfindung ein Verfahren zum selektiven anisotropen Entfernen mindestens eines Teils einer Siliziumschicht von einem siliziumhaltigen Substrat mit einer zwischen dem Substrat und der Siliziumschicht angeordneten und Praseodymoxid enthaltenden Zwischenschicht.The invention relates to a method for the selective removal of material containing praseodymium oxide from a silicon-containing substrate surface. The invention further relates to a method for removing light-sensitive lacquer from a substrate surface containing praseodymium oxide. Finally, the invention relates to a method for the selective anisotropic removal of at least part of a silicon layer from a silicon-containing substrate with an intermediate layer arranged between the substrate and the silicon layer and containing praseodymium oxide.
Mit dem Vordringen der CMOS-Technologie zu immer kleineren Bauelementabmessungen hat die Suche nach dielektrischen Materialien begonnen, die das standardmäßig verwendete Siliziumdioxid (SiO2) ersetzen können. In MOSFETs mit Gate-Längen von weniger 0,1 μm müsste ein Gate- Dielektrikum aus SiO2 eine Schichtdicke von weniger als 1 ,5 nm aufweisen. Bei einer solch geringen Schichtdicke treten durch das Dielektrikum hindurchfließende Leckströme auf, die einen MOSFET zur Anwendung in den meisten Schaltkreisen untauglich machen. Da der direkt tunnelnde Leckstrom expo- nentiell mit der Dicke des Dielektrikums abnimmt, kann ein dielektrisches Material mit größerer Dielektrizitätskonstante bei gleicher Gate-Kapazität die selbe dielektrische Eigenschaft wie SiO2 bei höherer Schichtdicke aufweisen.With the advance of CMOS technology to ever smaller component dimensions, the search for dielectric materials has begun that can replace the standard silicon dioxide (SiO 2 ). In MOSFETs with gate lengths of less than 0.1 μm would have to have a gate dielectric made of SiO 2 with a layer thickness of less than 1.5 nm. With such a small layer thickness, leakage currents flowing through the dielectric occur, which make a MOSFET unsuitable for use in most circuits. Since the directly tunneling leakage current exponentially decreases with the thickness of the dielectric, a dielectric material with a larger dielectric constant with the same gate capacitance can have the same dielectric property as SiO 2 with a higher layer thickness.
Aus der DE 100 39 327 A1 ist die Verwendung von Praseodymoxid, etwa in der Form von Pr2O3) bekannt. Praseodymoxid hat eine Dielektrizitätskonstante k von etwa 30 und erlaubt daher gegenüber einer äquivalenten SiO2-Schicht eine um den Faktor 30/3,9 erhöhte Schichtdicke. Damit können Tunnelströme unterdrückt werden.DE 100 39 327 A1 discloses the use of praseodymium oxide, for example in the form of Pr 2 O 3) . Praseodymium oxide has a dielectric constant k of about 30 and therefore allows a layer thickness increased by a factor of 30 / 3.9 compared to an equivalent SiO 2 layer. This means that tunnel currents can be suppressed.
Ein weitgehend unbekanntes Feld ist derzeit jedoch die prozesstechnische Integration von Praseodymoxid in moderne CMOS-Prozesse. Dies betrifft zum einen nasschemische Prozesse. Nasschemische Prozesse werden im CMOS- Verfahren zum Reinigen, zum Ätzen und zum Entfernen von Lackschichten benutzt. Es ist derzeit nichts über die Wechselwirkung dieser Standard- Prozessschritte mit Praseodymoxid bekannt. Im Laufe der Forschungsarbeiten, die der vorliegenden Erfindung zugrunde liegen, hat sich beispielsweise herausgestellt, dass Praseodymoxid sich im RCA-Standardreinigungsprozess auflöst. Ebenfalls hat es sich als nicht widerstandsfähig gegenüber einer ge- pufferten HF-Lösung erwiesen. Hier besteht ein der Erfindung zugrunde liegendes technisches Problem darin, ein zum selektiven Ätzen von Praseodymoxid auf siliziumhaltigen Oberflächen geeignetes nasschemisches Verfahren zu entwickeln. Die siliziumhaltige Oberfläche soll durch das Verfahren nicht angegriffen werden.A largely unknown field is currently the process engineering integration of praseodymium oxide in modern CMOS processes. On the one hand, this affects wet chemical processes. Wet chemical processes are used in the CMOS process for cleaning, etching and removing paint layers. Nothing is currently known about the interaction of these standard process steps with praseodymium oxide. In the course of the research work on which the present invention is based, it has been found, for example, that praseodymium oxide dissolves in the standard RCA cleaning process. It has also proven to be not resistant to a buffered HF solution. Here, a technical problem on which the invention is based is to develop a wet chemical process which is suitable for the selective etching of praseodymium oxide on silicon-containing surfaces. The method should not attack the silicon-containing surface.
Ein weiterer Problemkreis ist die Entfernung lichtempfindlicher Lacke im Rahmen der lithografischen Strukturbildung bei der Herstellung von Bauelementen. Die Lacke müssen nach einem Ätzschritt oder einem Implantationsschritt entfernt werden. Übliche nasschemische Methoden zur Lackentfernung arbei- ten mit Säuren, die Praseodymoxid auflösen. Hier gilt es, ein Verfahren zur Lackentfemung anzugeben, das eine unter dem Lack angeordnete Praseodymoxid-Schicht nicht beeinträchtigt.Another problem area is the removal of light-sensitive paints as part of the lithographic structure formation in the manufacture of components. The varnishes must be removed after an etching step or an implantation step. Common wet chemical paint removal methods work with acids that dissolve praseodymium oxide. Here is a procedure for Specify paint removal that does not impair a praseodymium oxide layer arranged under the paint.
Schließlich muss im Rahmen des CMOS-Prozesses ein Schritt des anisotro- pen reaktiven lonenätzens (reactive ion etching, RIE) von siliziumhaltigem Material durchgeführt werden, so beispielsweise bei der Ausbildung des aus polykristallinem Silizium gebildeten, so genannten Poly-Silizium-Gates eines MOSFET. Das technische Problem besteht hier darin, das Verfahren so auszubilden, dass der Ätzschritt auf dem Dielektrikum stoppt und so eine Be- Schädigung des Siliziumsubstrats vermieden wird.Finally, as part of the CMOS process, a step of anisotropic reactive ion etching (RIE) of silicon-containing material has to be carried out, for example when forming the so-called poly-silicon gate of a MOSFET, which is formed from polycrystalline silicon. The technical problem here is to design the method in such a way that the etching step on the dielectric stops and damage to the silicon substrate is avoided.
Aufgabe der Erfindung ist es, die genannten technischen Probleme zu lösen, die insbesondere bei der Integration von Praseodymoxid in CMOS-Prozesse auftreten.The object of the invention is to solve the technical problems mentioned, which occur in particular when integrating praseodymium oxide into CMOS processes.
Gemäß einem ersten Aspekt der Erfindung wird das Problem eines nasschemischen Prozesses gelöst durch ein Verfahren zum selektiven Entfernen von Praseodymoxid enthaltendem Material von einer siliziumhaltigen Substratoberfläche, bei dem das Praseodymoxid enthaltende Material in Kontakt mit einer sauren Lösung gebracht wird.According to a first aspect of the invention, the problem of a wet chemical process is solved by a method for the selective removal of material containing praseodymium oxide from a silicon-containing substrate surface, in which the material containing praseodymium oxide is brought into contact with an acidic solution.
Die Erfindung beruht auf der Erkenntnis, dass saure Lösungen geeignet sind, Praseodymoxid-Schichten selektiv von siliziumhaltigen Substratoberflächen zu entfernen.The invention is based on the knowledge that acidic solutions are suitable for selectively removing praseodymium oxide layers from silicon-containing substrate surfaces.
Besonders gute Erfolge wurden mit einer sauren Lösung erzielt, die Salzsäure (HCI) enthält. Ein Beispiel einer salzsäurehaltigen sauren Lösung ist die aus dem RCA-Reinigungsverfahren bekannte Lösung. Sie enthält eine 6:1 :1 Lösung von H2O:H2O2:HCI. Eine andere, geeignete saure Lösung enthält Phos- phorsäure (H3PO4). Es ist wichtig, dass die erfindungsgemäße saure Lösung Silizium nicht angreift.Particularly good results have been achieved with an acidic solution containing hydrochloric acid (HCI). An example of an acidic solution containing hydrochloric acid is the solution known from the RCA cleaning process. It contains a 6: 1: 1 solution of H 2 O: H 2 O 2 : HCl. Another suitable acidic solution contains phosphoric acid (H 3 PO 4 ). It is important that the acidic solution according to the invention does not attack silicon.
Ein besonders bevorzugtes Ausführungsbeispiel der Erfindung bildet ein Verfahren, bei dem saure Lösung Salzsäure mit einem Gewichtsanteil zwischen 0,6 % und 0,9 % enthält. Die besten Ergebnisse hinsichtlich der Atzgeschwin- digkeit wurden mit einer sauren Lösung erzielt, die Salzsäure mit einem Gewichtsanteil zwischen 0,7 % und 0,8 % enthält. Eine saure Lösung mit Salzsäure mit einem Gewichtsanteil von 0,75 %, die derzeit zur Prozessintegration am besten geeignet erscheint, weist eine Rate von 28 nm/min auf. Aufgrund der hohen, jedoch verfahrenstechnisch gut kontrollierbaren Ätzrate ist diese Ausführungsform des erfindungsgemäßen Verfahrens besonders gut geeignet, Praseodymoxid-Schichten selektiv von siliziumhaltigen Oberflächen zu entfernen.A particularly preferred embodiment of the invention is a method in which the acidic solution contains hydrochloric acid with a weight fraction between 0.6% and 0.9%. The best results regarding the etching speed were achieved with an acidic solution containing hydrochloric acid with a weight fraction between 0.7% and 0.8%. An acidic solution with hydrochloric acid with a weight fraction of 0.75%, which currently appears to be the most suitable for process integration, has a rate of 28 nm / min. Because of the high, but technically controllable etching rate, this embodiment of the method according to the invention is particularly well suited to selectively removing praseodymium oxide layers from silicon-containing surfaces.
Bevorzugt wird das erfindungsgemäße Verfahren dort angewendet, wo die Substratoberfläche überwiegend Silizium enthält oder sogar vollständig aus Silizium besteht. Es ist aber auch für siliziumhaltige Legierungen, wie beispielsweise Silizium-Germanium geeignet. Auch Substratoberflächen, die ganz oder abschnittsweise kohlenstoffdotiertes Silizium oder Silizium- Germanium enthalten, können mit dem erfindungsgemäßen Verfahren behandelt werden.The method according to the invention is preferably used where the substrate surface predominantly contains silicon or even consists entirely of silicon. However, it is also suitable for silicon-containing alloys, such as silicon germanium. Substrate surfaces which contain carbon-doped silicon or silicon germanium in whole or in sections can also be treated with the method according to the invention.
Wie sich aus der obigen Darstellung des erfindungsgemäßen Verfahrens ergibt, werden die besten Ergebnisse erzielt, wenn das selektiv zu entfernende Material überwiegend Praseodymoxid enthält oder vollständig aus Praseodymoxid besteht. Auch Materialien, die neben Praseodymoxid einen oder mehrere andere Bestandteile aufweisen, können mit dem erfindungsgemäßen Verfahren selektiv entfernt werden, da durch den Kontakt mit der sauren Lösung zumindest die Praseodymoxid-Bestandteile geätzt werden. Dadurch wird das Material strukturell so stark angegriffen, dass es von der siliziumhaltigen Substratoberfläche entfernt wird.As can be seen from the above illustration of the method according to the invention, the best results are achieved if the material to be selectively removed predominantly contains praseodymium oxide or consists entirely of praseodymium oxide. Materials which have one or more other constituents besides praseodymium oxide can also be selectively removed with the method according to the invention, since at least the praseodymium oxide constituents are etched by contact with the acidic solution. As a result, the material is so structurally attacked that it is removed from the silicon-containing substrate surface.
Das erfindungsgemäße Verfahren kann in unterschiedlichen Varianten durchgeführt werden. Sowohl eine Tauchätzung, bei der die Substratoberfläche mit dem Praseodymoxid enthaltenden Material zumindest teilweise in die säurehaltige Lösung eingetaucht wird, als auch eine Sprühätzung, bei der die Substratoberfläche mit dem Praseodymoxid enthaltenden Material mit der säurehaltigen Lösung besprüht wird, sind denkbar. Gemäß einem weiteren Aspekt der Erfindung, wird das Problem der Lackentfernung gelöst durch ein Verfahren zum Entfernen von lichtempfindlichem Lack von einer Praseodymoxid enthaltenden Substratoberfläche, bei dem der lichtempfindliche Lack mit einem organischen Lösungsmittel in Kontakt ge- bracht wird.The method according to the invention can be carried out in different variants. Both dip etching, in which the substrate surface with the material containing praseodymium oxide is at least partially immersed in the acidic solution, and spray etching, in which the substrate surface is sprayed with the material containing praseodymium oxide with the acidic solution, are conceivable. According to a further aspect of the invention, the problem of lacquer removal is solved by a method for removing light-sensitive lacquer from a substrate surface containing praseodymium oxide, in which the light-sensitive lacquer is brought into contact with an organic solvent.
Die Erfindung beruht auf der Erkenntnis, dass nur organische Lösungsmittel geeignet sind, den Lack zu entfernen, ohne die Praseodymoxid-Schicht zu beeinträchtigen. Als geeignetes Lösungsmittel wird in einem Ausführungsbei- spiel der Erfindung ein azetonhaltiges Lösungsmittel verwendet. Es kann in einer bevorzugten Ausführungsform auch reines Azeton verwendet werden.The invention is based on the finding that only organic solvents are suitable for removing the lacquer without impairing the praseodymium oxide layer. In one exemplary embodiment of the invention, an acetone-containing solvent is used as a suitable solvent. In a preferred embodiment, pure acetone can also be used.
Bei einem weiteren Ausführungsbeispiel der Erfindung wird ein organisches Lösungsmittel verwendet, das unter dem Namen AZ100 von der Firma Clari- ant (http://www.clariant.com) vertrieben wird. Auch dieses kann rein oder in Mischung mit einem anderen organischen Lösungsmittel verwendet werden.In a further exemplary embodiment of the invention, an organic solvent is used, which is sold under the name AZ100 by the Clariant company (http://www.clariant.com). This can also be used neat or in a mixture with another organic solvent.
Die Lackentfernung erfolgt bei dem erfindungsgemäßen Verfahren nach ansonsten verfahrenstechnisch an sich bekannten Methoden. Insbesondere wird vorzugsweise ein Tauchverfahren zum Entfernen des Lackes angewendet. Dabei wird zumindest die Substratoberfläche mit dem Lack oder aber das gesamte Substrat in das organische Lösungsmittel eingetaucht. Unter der Lackschicht liegende Praseodymoxid oder Silizium enthaltende Schichten werden nicht angegriffenIn the process according to the invention, the lacquer is removed by methods which are otherwise known per se in process engineering. In particular, an immersion process is preferably used to remove the paint. At least the substrate surface with the lacquer or the entire substrate is immersed in the organic solvent. Praseodymium oxide or layers containing silicon underneath the lacquer layer are not attacked
Neben nasschemischen Methoden zur Lackentfernung kann zum Ätzen des Lackes auch ein Sauerstoffplasma zum Einsatz kommen. Es hat sich jedoch herausgestellt, dass die im Plasma vorhandenen Sauerstoffradikale auf die Praseodymoxid/Silizium(001)-Grenzfläche einen negativen Einfluss haben. Daher wird die Verwendung eines Sauerstoffplasmas nicht bevorzugt.In addition to wet chemical methods for removing paint, an oxygen plasma can also be used to etch the paint. However, it has been found that the oxygen radicals present in the plasma have a negative influence on the praseodymium oxide / silicon (001) interface. Therefore, the use of an oxygen plasma is not preferred.
Nach einem dritten Aspekt der Erfindung wird das Problem der Entwicklung eines selektiven RIE-Prozesses durch ein Verfahren zum selektiven anisotropen Entfernen mindestens eines Teils einer Silizium enthaltenden Schicht von einem siliziumhaltigen Substrat mit einer zwischen dem Substrat und der Sili- ziumschicht angeordneten und Praseodymoxid enthaltenden Zwischenschicht gelöst, bei dem ein aus einem Reaktionsgas unter elektrischer Wechselspannung gebildetes Plasma in einer Reaktionskammer mit dem Substrat in Berührung tritt, dadurch gekennzeichnet, dass das Reaktionsgas SF6 CI2 enthält.According to a third aspect of the invention, the problem of developing a selective RIE process by a method for selectively anisotropically removing at least part of a silicon-containing layer from a silicon-containing substrate with a layer between the substrate and the silicon Intermediate layer arranged zium layer and containing praseodymium oxide, in which a plasma formed from a reaction gas under electrical alternating voltage comes into contact with the substrate in a reaction chamber, characterized in that the reaction gas contains SF 6 CI 2 .
Das erfindungsgemäße Verfahren vermeidet eine Beschädigung des Siliziumsubstrates. Es eignet sich insbesondere zur Ätzung einer Polysilizium-Gate- Struktur. Die Selektivität des Ätzprozesses ist gegenüber dem Polysilizium- Gate 300 mal größer als gegenüber Praseodymoxid. Neben dem RIE von rei- nem Silizium eignet sich das erfindungsgemäße Verfahren auch zum Ätzen von siliziumhaltigen Legierungen.The method according to the invention avoids damage to the silicon substrate. It is particularly suitable for etching a polysilicon gate structure. The selectivity of the etching process is 300 times greater than that of praseodymium oxide compared to the polysilicon gate. In addition to the RIE of pure silicon, the method according to the invention is also suitable for etching silicon-containing alloys.
Die Verwendung von SF6/CI2 als Reaktionsgas ermöglicht die Verwendung eines ansonsten standardmäßigen RIE-Prozesses. The use of SF 6 / CI 2 as the reaction gas enables the use of an otherwise standard RIE process.

Claims

Patentansprüche claims
1. Verfahren zum selektiven Entfernen von Praseodymoxid enthaltendem Material von einer siliziumhaltigen Substratoberfläche, bei dem das Pra- seodymoxid enthaltende Material in Kontakt mit einer sauren Lösung gebracht wird.1. Method for the selective removal of praseodymium oxide-containing material from a silicon-containing substrate surface, in which the material containing praseodymium oxide is brought into contact with an acidic solution.
2. Verfahren nach Anspruch 1 , bei dem die saure Lösung Salzsäure (HCI) enthält.2. The method of claim 1, wherein the acidic solution contains hydrochloric acid (HCl).
3. Verfahren nach Anspruch 2, bei dem die saure Lösung Salzsäure mit einem Gewichtsanteil zwischen 0,6% und 0,9% enthält.3. The method of claim 2, wherein the acidic solution contains hydrochloric acid in a weight proportion between 0.6% and 0.9%.
4. Verfahren nach Anspruch 3, bei dem die saure Lösung Salzsäure mit einem Gewichtsanteil zwischen 0,7% und 0,8% enthält.4. The method according to claim 3, wherein the acidic solution contains hydrochloric acid in a weight fraction between 0.7% and 0.8%.
5. Verfahren nach Anspruch 3, bei dem die saure Lösung Salzsäure mit einem Gewichtsanteil von 0,75 % enthält.5. The method of claim 3, wherein the acidic solution contains hydrochloric acid in a weight fraction of 0.75%.
6. Verfahren nach einem der vorstehenden Ansprüche, bei dem die Substratoberfläche überwiegend Silizium enthält.6. The method according to any one of the preceding claims, wherein the substrate surface predominantly contains silicon.
7. Verfahren nach einem der vorstehenden Ansprüche, bei dem die Substratoberfläche zusätzlich Germanium enthält.7. The method according to any one of the preceding claims, wherein the substrate surface additionally contains germanium.
8. Verfahren nach einem der Ansprüche 1 bis 5, bei dem die Substratober- fläche aus Silizium besteht.8. The method according to any one of claims 1 to 5, wherein the substrate surface consists of silicon.
9. Verfahren nach einem der vorstehenden Ansprüche, bei dem das Praseodymoxid enthaltende Material überwiegend Praseodymoxid enthält.9. The method according to any one of the preceding claims, wherein the material containing praseodymium oxide predominantly contains praseodymium oxide.
10. Verfahren nach einem der Ansprüche 1 bis 8, bei dem das Praseodymoxid enthaltende Material aus Praseodymoxid besteht. 10. The method according to any one of claims 1 to 8, wherein the praseodymium oxide-containing material consists of praseodymium oxide.
11. Verfahren nach einem der vorstehenden Ansprüche, bei dem die Substratoberfläche mit dem Praseodymoxid enthaltenden Material zumindest teilweise in die saure Lösung eingetaucht wird.11. The method according to any one of the preceding claims, wherein the substrate surface with the praseodymium oxide-containing material is at least partially immersed in the acidic solution.
12. Verfahren nach einem der vorstehenden Ansprüche, bei dem die Sub- stratoberfläche mit dem Praseodymoxid enthaltenden Material mit der sauren Lösung benetzt oder besprüht wird.12. The method according to any one of the preceding claims, wherein the substrate surface with the praseodymium oxide-containing material is wetted or sprayed with the acidic solution.
13. Verfahren zum Entfernen von lichtempfindlichem Lack von einer Praseodymoxid enthaltenden Substratoberfläche, bei dem der lichtempfindliche Lack mit einem organischen Lösungsmittel in Kontakt gebracht wird.13. A method for removing photosensitive varnish from a substrate surface containing praseodymium oxide, in which the photosensitive varnish is brought into contact with an organic solvent.
14. Verfahren nach Anspruch 13, bei dem das organische Lösungsmittel Azeton enthält.14. The method of claim 13, wherein the organic solvent contains acetone.
15. Verfahren nach Anspruch 13, bei dem das organische Lösungsmittel Azeton ist.15. The method of claim 13, wherein the organic solvent is acetone.
16. Verfahren nach Anspruch 13 oder 14, bei dem das organische Lö- sungsmittel AZ100 wet remover enthält.16. The method of claim 13 or 14, wherein the organic solvent contains AZ100 wet remover.
17. Verfahren nach Anspruch 13, bei dem das organische Lösungsmittel AZ100 wet remover ist.17. The method of claim 13, wherein the organic solvent is AZ100 wet remover.
18. Verfahren zum selektiven anisotropen Entfernen mindestens eines Teils einer Silizium enthaltenden Schicht von einem siliziumhaltigen Substrat mit einer zwischen dem Substrat und der Siliziumschicht angeordneten und Praseodymoxid enthaltenden Zwischenschicht, bei dem ein aus einem Reaktionsgas unter elektrischer Wechselspannung gebildetes Plasma in einer Reaktionskammer mit dem Substrat in Berührung tritt, dadurch gekennzeichnet, dass das Reaktionsgas SF6/CI2 enthält.18. A method for the selective anisotropic removal of at least part of a silicon-containing layer from a silicon-containing substrate with an intermediate layer arranged between the substrate and the silicon layer and containing praseodymium oxide, in which a plasma formed from a reaction gas under alternating electrical voltage in a reaction chamber with the substrate in Contact occurs, characterized in that the reaction gas contains SF 6 / CI 2 .
19. Verfahren nach Anspruch 18, dadurch gekennzeichnet, dass das Reaktionsgas aus SF6/CI2 besteht. 19. The method according to claim 18, characterized in that the reaction gas consists of SF 6 / CI 2 .
PCT/EP2003/010413 2002-09-23 2003-09-18 Method for the production of an electronic component comprising a praseodymium oxide layer WO2004030068A1 (en)

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