EP0000701A2 - Process for the removal of silicon dioxide residue from a semiconductor surface - Google Patents
Process for the removal of silicon dioxide residue from a semiconductor surface Download PDFInfo
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- EP0000701A2 EP0000701A2 EP7878100336A EP78100336A EP0000701A2 EP 0000701 A2 EP0000701 A2 EP 0000701A2 EP 7878100336 A EP7878100336 A EP 7878100336A EP 78100336 A EP78100336 A EP 78100336A EP 0000701 A2 EP0000701 A2 EP 0000701A2
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- Prior art keywords
- silicon dioxide
- semiconductor surface
- phosphoric acid
- polishing
- solution
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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
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
Definitions
- the invention relates to a method for removing silicon dioxide residues from a semiconductor surface after polishing with a silicon dioxide-containing polishing agent.
- polishing with silicon dioxide is an example of a typical polishing process. This process uses a polishing slurry containing an abrasive colloidal silicon dioxide, sodium dichloroisocyanurate as an oxidizing agent and sodium carbonate as a basic component. The pH of the polishing slurry is below 10. After polishing, it is necessary to clean the polished surface to remove the polishing slurry and other surface contaminants with a minimum of chemical or mechanical surface damage.
- the object of the invention is to provide an environmentally friendly, safe and effective method for removing silicon dioxide polishing materials while maintaining a clean, hydrophilic, undamaged semiconductor surface.
- the object of the invention is achieved by a method of the type mentioned at the outset, which is characterized in that the semiconductor surface is treated with an aqueous phosphoric acid solution and then rinsed with water and an aqueous ammonium hydroxide solution.
- the semiconductor surface is additionally treated with an aqueous sulfuric acid solution and then rinsed.
- the aqueous silica-based slurry used to polish semiconductor surfaces contains colloidal silica as the abrasive material, an oxidizing agent such as sodium dichloroisocyanurate and a base such as sodium carbonate.
- the surface After polishing the semiconductor surface with the silicon dioxide slurry, the surface is contaminated with a residue of colloidal silicon dioxide, amorphous silicon dioxide, sodium carbonate and residues of the polishing cloth. Rinsing with water alone is not enough to remove the impurities.
- the hydrophobic nature of the surface is converted to a hydrophilic one, which is probably due to the hydrolysis of the siloxane groups on the silicon surface, which takes place in an acid medium.
- Surface hydrolysis and dissolution are accelerated by a sulfuric acid treatment as shown in Example 1.
- the method allows the semiconductors to be stored prior to cleaning by placing them in a dilute aqueous solution of phosphoric acid without water stains or fog on the semiconductor surface after cleaning.
- Suitable phosphoric acid concentrations in water are in the range from 10 to 50% by weight, preferably in the range from 20 to 30% by weight.
- a phosphoric acid cleaning solution for a long time (example, 24 hours) and then easily and effectively cleaned by the method of the invention to obtain a fog-free surface.
- the substrates are first sprayed or immersed in an aqueous phosphoric acid solution at ambient temperatures (20 to 30 ° C.) for about 5 to 10 minutes and then rinsed in water to remove the loose particles and the phosphoric acid remove solution. Thereafter, the substrates are preferably treated with a dilute (20 to 30% by weight) aqueous sulfuric acid solution which brings about the dissolution of any silicon phosphates and favors the surface hydrolysis.
- the sulfuric acid solution can be added to the phosphoric acid solution.
- the water-rinsed substrates are rinsed with dilute aqueous ammonium hydroxide solution, which is about 3 to 5% by weight, (immersed or sprayed).
- a complexing agent can also be added to the ammonium hydroxide solution to remove the Favor ion removal.
- the semiconductor body is then rinsed in water and cleaned by brushing in water.
- the concentrations are in parts by weight, unless stated otherwise.
- Freshly polished and rinsed silicon wafers are placed in an aqueous 21% phosphoric acid solution for 10 minutes and then removed and rinsed in running deionized water for two minutes.
- the wafers are placed in 20% by weight aqueous sulfuric acid for five minutes, rinsed with deionized water for two minutes, and then rinsed with a 3% aqueous ammonium hydroxide solution for 30 seconds. They are then sprayed with deionized water and spun dry in a hot nitrogen atmosphere. This process is carried out in an automatic rinsing-drying device.
- the wafers are cleaned by brushing or with a felt with deionized water. Examination of the surface under a bright lamp showed that none Silicon dioxide or other particulate contaminants were present.
- the above-mentioned method can be modified in such a way that two steps are eliminated when using an aqueous solution containing 21% by weight phosphoric acid and 20% by weight sulfuric acid in one step. This eliminates the need for separate use of sulfuric acid and the second water rinse.
- Silicon wafers that have been polished with a silicon dioxide polishing slurry and then rinsed with water are removed from the polishing machine and placed in a 20% by weight aqueous phosphoric acid solution at room temperature for five minutes without prior drying.
- the wafers are removed from the solution and rinsed with deionized water for three minutes and then sprayed with an aqueous 3% by weight ammonium hydroxide solution and then with deionized water in a sprayer for 30 seconds and then spun in a hot nitrogen atmosphere.
- the entire rinsing process is carried out in an automatic spray drying machine and takes approximately 10 minutes.
- the wafers are hydrophilic (i.e. water wets the surface).
- the wafer surfaces are clean and without fog.
- An emission spectrographic analysis on the cleaned wafers shows negligible amounts of Al, Ca, Cr, Cu, Fe, Mg, Na and Ti.
- the described method leads to polished semiconductor surfaces which are clean, hydrophilic and without fog.
- the surfaces are not degraded by the cleaning process and only environmentally friendly and hygienic materials are used in the process.
- the semiconductor materials can be stored in dilute phosphoric acid solution for up to 24 hours before cleaning, without the surface being damaged in any way. Only a light brush cleaning is required to remove any particles from the cleaned surfaces.
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Abstract
Die Erfindung betrifft ein Verfahren zur Entfernung von Siliciumdioxidrückständen von einer Halbleiteroberfläche. Halbleitermaterialien werden nach dem Polieren mit einem siliciumdioxidhaltigen Poliermittel mit einer wässrigen Phosphorsäurelösung und gegebenenfalls einer Schwefelsäurelösung behandelt und mit einer Ammoniumhydroxidlösung und deionisiertem Wasser gespült, um kolloidales Siliciumdioxid zu lösen und von der Halbleiteroberfläche zu entfernen. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß kolloidale oder amorphe Siliciumdioxidrückstände von der Halbleiteroberfläche entfernt werden.The invention relates to a method for removing silicon dioxide residues from a semiconductor surface. After polishing with a silicon dioxide-containing polishing agent, semiconductor materials are treated with an aqueous phosphoric acid solution and optionally with a sulfuric acid solution and rinsed with an ammonium hydroxide solution and deionized water in order to dissolve and remove colloidal silicon dioxide from the semiconductor surface. Process according to claims 1 to 5, characterized in that colloidal or amorphous silicon dioxide residues are removed from the semiconductor surface.
Description
Die Erfindung betrifft ein Verfahren zur Entfernung von Siliciumdioxidrückständen von einer Halbleiteroberfläche nach dem Polieren mit einem siliciumdioxidhaltigen Poliermittel.The invention relates to a method for removing silicon dioxide residues from a semiconductor surface after polishing with a silicon dioxide-containing polishing agent.
Im Zuge der Mikrominiaturisierung elektronischer Schaltkreise hat das Bedürfnis nach glatten und reinen Halbleiteroberflächen ohne Beschädigungen erhebliche Bedeutung erlangt. Glatte polierte Oberflächen werden durch Anwendung eines Polierschlamms erhalten. Das Polieren mit Siliciumdioxid ist ein Beispiel für ein typisches Polierverfahren. Bei diesem Verfahren wird ein Polierschlamm mit einem Gehalt an einem abtragenden kolloidalen Siliciumdioxid, Natriumdichlorisocyanurat als Oxidationsmittel und Natriumcarbonat als basischem Bestandteil verwendet. Der pH-Wert des Polierschlamms liegt unterhalb 10. Nach dem Polieren ist es erforderlich, die polierte Oberfläche zu reinigen, um den Polierschlamm und andere Oberflächenverunreinigungen bei einem Minimum an chemischer oder mechanischer Oberflächenbeschädigung zu entfernen.In the course of microminiaturization of electronic circuits, the need for smooth and pure semiconductor surfaces without damage has become of considerable importance. Smooth polished surfaces are obtained using a polishing slurry. Polishing with silicon dioxide is an example of a typical polishing process. This process uses a polishing slurry containing an abrasive colloidal silicon dioxide, sodium dichloroisocyanurate as an oxidizing agent and sodium carbonate as a basic component. The pH of the polishing slurry is below 10. After polishing, it is necessary to clean the polished surface to remove the polishing slurry and other surface contaminants with a minimum of chemical or mechanical surface damage.
Nach der Beendigung des Polierverfahrens mit Siliciumdioxid, sind folgende Materialien von der Halbleiteroberfläche zu entfernen, um eine reine Oberfläche zu erhalten:
- 1. kolloidales Siliciumdioxid;
- 2. Natriumdichlorisocyanurat und dessen'Reaktionsprodukte mit Natriumcarbonat;
- 3. Natriumcarbonat;
- 4. amorphes Siliciumdioxid;
- 5. andere metallische Verunreinigungen, die sich aus den Komponenten des Polierschlamms auf der Halbleiteroberfläche abgeschieden haben.
- 1. colloidal silicon dioxide;
- 2. Sodium dichloroisocyanurate and its reaction products with sodium carbonate;
- 3. sodium carbonate;
- 4. amorphous silicon dioxide;
- 5. other metallic contaminants that have deposited on the semiconductor surface from the components of the polishing slurry.
Bisher wurden verschiedene mechanische und chemische Verfahren angewendet, um die mit Siliciumdioxid oder einem metalloxidhaltigen Schlamm polierten Wafer zu reinigen. Diese Verfahren verursachen mechanische Beschädigungen, beachtliche Änderungen der Oberflächencharakteristika oder werden unter Anwendung von Chemikalien durchgeführt, die nicht umweltfreundlich und/ oder aus hygienischen Gründen nicht brauchbar sind.To date, various mechanical and chemical processes have been used to clean the wafers polished with silicon dioxide or a metal oxide-containing slurry. These processes cause mechanical damage, considerable changes in the surface characteristics or are carried out using chemicals which are not environmentally friendly and / or are not usable for hygienic reasons.
In dem in der deutschen Offenlegungsschrift 27 06 519 beschriebenen Verfahren wird zur Reinigung der Halbleiteroberfläche eine Behandlung mit einem Oxidationsmittel, beispielsweise NaClO, gefolgt von einer Spülung mit Ammoniumhydroxid durchgeführt. In einem anderen Verfahren werden quaternäre Ammoniumsalze angewendet, um reine hydrophobe Halbleiteroberflächen ohne Beschädigung der Oberfläche zu erhalten.In the method described in German Offenlegungsschrift 27 06 519, treatment with an oxidizing agent, for example NaClO, is carried out to clean the semiconductor surface, followed by rinsing with ammonium hydroxide. Another method uses quaternary ammonium salts to obtain pure hydrophobic semiconductor surfaces without damaging the surface.
Aufgabe der Erfindung ist die Bereitstellung eines umwelt freundlichen, sicheren und effektiven Verfahrens zur Entfernung von Siliciumdioxid-Poliermaterialien unter Erhalt einer reinen, hydrophilen, nicht beschädigten Halbleiteroberfläche.The object of the invention is to provide an environmentally friendly, safe and effective method for removing silicon dioxide polishing materials while maintaining a clean, hydrophilic, undamaged semiconductor surface.
Die Aufgabe der Erfindung wird gelöst durch ein Verfahren der eingangs genannten Art, das dadurch gekennzeichnet ist, daß die Halbleiteroberfläche mit einer wässrigen Phosphorsäurelösung behandelt und dann mit Wasser und einer wässrigen Ammoniumhydroxidlösung gespült wird.The object of the invention is achieved by a method of the type mentioned at the outset, which is characterized in that the semiconductor surface is treated with an aqueous phosphoric acid solution and then rinsed with water and an aqueous ammonium hydroxide solution.
In einer vorteilhaften Ausgestaltung der Erfindung wird die Halbleiteroberfläche nach der Behandlung mit Phosphorsäure zusätzlich mit einer wässrigen Schwefelsäurelösung behandelt und dann gespült.In an advantageous embodiment of the invention, after the treatment with phosphoric acid, the semiconductor surface is additionally treated with an aqueous sulfuric acid solution and then rinsed.
Die Erfindung wird anhand der nachfolgenden speziellen Beschreibung und der Ausführungsbeispiele näher erläutert.The invention is explained in more detail on the basis of the following special description and the exemplary embodiments.
Der wässrige Schlamm auf Siliciumdioxidbasis, der zum Polieren von Halbleiteroberflächen verwendet wird, enthält kolloidales Siliciumdioxid als abtragendes Material, ein Oxidationsmittel wie Natriumdichlorisocyanurat und eines Base wie Natriumcarbonat.The aqueous silica-based slurry used to polish semiconductor surfaces contains colloidal silica as the abrasive material, an oxidizing agent such as sodium dichloroisocyanurate and a base such as sodium carbonate.
Nach dem Polieren der Halbleiteroberfläche mit dem Siliciumdioxidschlamm ist die Oberfläche mit einem Rückstand aus kolloidalem Siliciumdioxid, amorphem Siliciumdioxid, Natriumcarbonat und Rückständen des Poliertuchs verunreinigt. Eine Spülung mit Wasser allein genügt nicht zur Entfernung der Verunreinigungen.After polishing the semiconductor surface with the silicon dioxide slurry, the surface is contaminated with a residue of colloidal silicon dioxide, amorphous silicon dioxide, sodium carbonate and residues of the polishing cloth. Rinsing with water alone is not enough to remove the impurities.
Es ist bekannt, daß Siliciumdioxid mit Phosphorsäure bei hohen Temperaturen (über 200 °C) reagiert unter Ausbildung verschiedener Siliciumphosphate je nach den Reaktionsbedingungen (s. H. R. Levi et al; Z. Krist 92, 191 1935). Es ist auch bekannt, daß festes Silicagel mit verdünnter Phosphorsäure reagiert unter Ausbildung eines Oberflächenfilms, welcher die Löslichkeit des Siliciumdioxids sowohl in Wasser wie auch in Phorphorsäure verzögert (s. B. M. Mitsynk, Zh. Neorg Khim, 17 903 (1972)). Überraschend im Hinblick auf diese Veröffentlichungen wurde nunmehr gefunden, daß kolloidales Siliciumdioxid anders als festes Siliciumdioxid sich schnell in verdünnter Phosphorsäure bei Zimmertemperatur löst, so daß die Wafer leicht und ohne Beschädigung gereinigt werden können. Die hydrophobe Natur der Oberfläche wird in eine hydrophile umgewandelt, was wahrscheinlich auf die in saurem Medium stattfindende Hydrolyse der Siloxangruppen an der Siliciumoberfäche zurückzuführen ist. Die Hydrolyse an der Oberfläche und das Auflösen werden durch eine Schwefelsäurebehandlung, wie in Beispiel 1 dargestellt ist, beschleunigt. Das Verfahren gestattet die Aufbewahrung der Halbleiter vor der Reinigung, indem sie in eine verdünnte wässrige Phosphorsäurelösung gebracht werden, ohne daß Wasserflecken oder Schleier auf der Halbleiteroberfläche im Anschluß an die Reinigung gebildet werden.It is known that silicon dioxide reacts with phosphoric acid at high temperatures (above 200 ° C.) with the formation of various silicon phosphates depending on the reaction conditions (see HR Levi et al; Z. Krist 92, 191 1935). It is also known that solid silica gel reacts with dilute phosphoric acid to form a surface film that increases the solubility of the silicon dioxides delayed both in water and in phosphorus acid (see BM Mitsynk, Zh. Neorg Khim, 17 903 (1972)). Surprisingly in view of these publications, it has now been found that colloidal silicon dioxide, unlike solid silicon dioxide, quickly dissolves in dilute phosphoric acid at room temperature, so that the wafers can be cleaned easily and without damage. The hydrophobic nature of the surface is converted to a hydrophilic one, which is probably due to the hydrolysis of the siloxane groups on the silicon surface, which takes place in an acid medium. Surface hydrolysis and dissolution are accelerated by a sulfuric acid treatment as shown in Example 1. The method allows the semiconductors to be stored prior to cleaning by placing them in a dilute aqueous solution of phosphoric acid without water stains or fog on the semiconductor surface after cleaning.
Geeignete Phosphorsäurekonzentrationen in Wasser liegen im Bereich von 10 bis 50 Gew.%, vorzugsweise im Bereich von 20 bis 30 Gew.%. Nachdem der Poliervorgang beendigt ist, werden die Halbleitersubstrate aus der Poliermaschine entfernt, ohne daß man sie trocknen läßt.Suitable phosphoric acid concentrations in water are in the range from 10 to 50% by weight, preferably in the range from 20 to 30% by weight. After the polishing process is completed, the semiconductor substrates are removed from the polishing machine without being allowed to dry.
Sie können dann unmittelbar gereinigt oder in einer Phosphorsäurereinigungslösung für längere Zeit (beispiels weise 24 Stunden) aufbewahrt und danach leicht und wirkungsvoll nach dem erfindungsgemäßen Verfahren gereinigt werden unter Erhalt einer schleierfreien Oberfläche. Zur Reinigung der Substrate werden diese zuerst besprüht oder etwa 5 bis 10 Minuten lang bei Umgebungstemperaturen (20 bis 30 °C) in eine wässrige Phosphorsäurelösung getaucht und dann in Wasser gespült, um die lose anhaftenden Teilchen und die Phosphorsäurelösung zu entfernen. Danach werden die Substrate vorzugsweise mit einer verdünnten (20 bis 30 gew.%igen) wässrigen Schwefelsäurelösung behandelt, welche die Auflösung irgendwelcher Siliciumphosphate bewirkt und die Oberflächenhydrolyse begünstigt. Alternativ hierzu kann die Schwefelsäurelösung zu der Phosphorsäurelösung zugegeben werden. Für den Fall, daß Schwermetallverunreinigungen vorhanden sind, werden die mit Wasser gespülten Substrate mit verdünnter wässriger Ammoniumhydroxidlösung, die etwa 3 bis 5 gew.%ig ist, gespült, (getaucht oder besprüht) Ein Komplexbildner kann auch zu der Ammoniumhydroxidlösung zugegeben werden, um die Entfernung der Ionen zu begünstigen. Der Halbleiterkörper wird dann in Wasser gespült und durch Bürsten in Wasser gereinigt.You can then immediately cleaned or stored in a phosphoric acid cleaning solution for a long time (example, 24 hours) and then easily and effectively cleaned by the method of the invention to obtain a fog-free surface. To clean the substrates, they are first sprayed or immersed in an aqueous phosphoric acid solution at ambient temperatures (20 to 30 ° C.) for about 5 to 10 minutes and then rinsed in water to remove the loose particles and the phosphoric acid remove solution. Thereafter, the substrates are preferably treated with a dilute (20 to 30% by weight) aqueous sulfuric acid solution which brings about the dissolution of any silicon phosphates and favors the surface hydrolysis. Alternatively, the sulfuric acid solution can be added to the phosphoric acid solution. In the event that heavy metal contaminants are present, the water-rinsed substrates are rinsed with dilute aqueous ammonium hydroxide solution, which is about 3 to 5% by weight, (immersed or sprayed). A complexing agent can also be added to the ammonium hydroxide solution to remove the Favor ion removal. The semiconductor body is then rinsed in water and cleaned by brushing in water.
In den nachfolgenden Ausführungsbeispielen sind die Konzentrationen, wenn nicht anders angegeben, in Gewichtsteilen.In the following exemplary embodiments, the concentrations are in parts by weight, unless stated otherwise.
Frisch polierte und gespülte Siliciumwafer werden 10 Minu ten lang in eine wässrige, 21 %ige Phosphorsäurelösung gegeben und dann entfernt und zwei Minuten lang in fliessendem deionisiertem Wasser gespült. Die Wafer werden fünf Minuten lang in 20 gew.%ige wässrige Schwefelsäure gegeben, zwei Minuten lang mit deionisiertem Wasser und anschließend 30 Sekunden lang mit einer 3 %igen wässrigen Ammoniumhydroxidlösung gespült. Sie werden dann mit deionisiertem Wasser besprüht und in heißer Stickstoffatmosphäre trockengeschleudert. Dieser Vorgang wird in einer automatischen Spül-Trocknungsvorrichtung durchgeführt. Die Wafer werden durch Bürsten oder mit einem Filz mit deionisiertem Wasser gereinigt. Die Prüfung der Oberfläche unter einer hellen Lampe ergab, daß kein Siliciumdioxid oder andere teilchenförmige Verunreinigungen vorhanden waren.Freshly polished and rinsed silicon wafers are placed in an aqueous 21% phosphoric acid solution for 10 minutes and then removed and rinsed in running deionized water for two minutes. The wafers are placed in 20% by weight aqueous sulfuric acid for five minutes, rinsed with deionized water for two minutes, and then rinsed with a 3% aqueous ammonium hydroxide solution for 30 seconds. They are then sprayed with deionized water and spun dry in a hot nitrogen atmosphere. This process is carried out in an automatic rinsing-drying device. The wafers are cleaned by brushing or with a felt with deionized water. Examination of the surface under a bright lamp showed that none Silicon dioxide or other particulate contaminants were present.
Das zuvor angegebene Verfahren kann dahingehend modifiziert werden, daß zwei Schritte eliminiert werden bei Anwendung einer wässrigen Lösung mit einem Gehalt an 21 Gew.% Phosphorsäure und 20 Gew.% Schwefelsäure in einem Schritt. Dies macht die separate Anwendung der Schwefelsäure und die zweite Wasserspülung überflüssig.The above-mentioned method can be modified in such a way that two steps are eliminated when using an aqueous solution containing 21% by weight phosphoric acid and 20% by weight sulfuric acid in one step. This eliminates the need for separate use of sulfuric acid and the second water rinse.
Siliciumwafer, die mit einem Siliciumdioxidpolierschlamm poliert und dann mit Wasser gespült wurden, werden von der Poliermaschine entfernt und ohne vorherige Trocknung fünf Minuten lang bei Zimmertemperatur in eine 20 gew.%- ige wässrige Phosphorsäurelösung gegeben. Die Wafer werden aus der Lösung entfernt und drei Minuten lang mit deionisiertem Wasser gespült und dann 30 Sekunden lang in einer Sprühvorrichtung mit einer wässrigen 3 gew.%igen Ammoniumhydroxidlösung und anschließend mit deionisiertem Wasser besprüht und dann in heißer Stickstoffatmosphäre durch Schleudern getrocknet. Der gesamte Spülprozeß wird in einem Sprühtrocknungsautomaten durchgeführt und dauert ungefähr 10 Minuten. Die Wafer sind nach dem Reinigungsprozeß hydrophil (d.h. Wasser benetzt die Oberfläche). Die Waferoberflächen sind rein und ohne Schleier. Eine emissionsspektrographische Analyse an den gereinigten Wafern zeigt vernachlässigbare Mengen von Al, Ca, Cr, Cu, Fe, Mg, Na und Ti.Silicon wafers that have been polished with a silicon dioxide polishing slurry and then rinsed with water are removed from the polishing machine and placed in a 20% by weight aqueous phosphoric acid solution at room temperature for five minutes without prior drying. The wafers are removed from the solution and rinsed with deionized water for three minutes and then sprayed with an aqueous 3% by weight ammonium hydroxide solution and then with deionized water in a sprayer for 30 seconds and then spun in a hot nitrogen atmosphere. The entire rinsing process is carried out in an automatic spray drying machine and takes approximately 10 minutes. After the cleaning process, the wafers are hydrophilic (i.e. water wets the surface). The wafer surfaces are clean and without fog. An emission spectrographic analysis on the cleaned wafers shows negligible amounts of Al, Ca, Cr, Cu, Fe, Mg, Na and Ti.
Der zuvor angegebene Reinigungsprozeß wurde an Wafern wiederholt, welche 24 Stunden lang in der Reinigungslösung aufbewahrt worden waren. Er führte zu reinen Oberflächen ohne Spuren von Wasser und Flecken auf den Wafern.The above cleaning process was repeated on wafers which had been kept in the cleaning solution for 24 hours. It led to pure Surfaces without traces of water and stains on the wafers.
Das beschriebene Verfahren führt zu polierten Halbleiteroberflächen, welche sauber, hydrophil und ohne Schleier sind. Die Oberflächen werden durch den Reinigungsprozeß nicht abgebaut, und in dem Verfahren werden nur umweltfreundliche und hygienische Materialien verwendet. Die Halbleitermaterialien können vor der Reinigung bis zu 24 Stunden in verdünnter Phosphorsäurelösung aufbewahrt werden, ohne daß die Oberfläche in irgendeiner Weise beschädigt wird. Es ist nur eine leichte Bürstenreinigung erforderlich, um irgendwelche Partikel von den gereinigten Oberflächen zu entfernen.The described method leads to polished semiconductor surfaces which are clean, hydrophilic and without fog. The surfaces are not degraded by the cleaning process and only environmentally friendly and hygienic materials are used in the process. The semiconductor materials can be stored in dilute phosphoric acid solution for up to 24 hours before cleaning, without the surface being damaged in any way. Only a light brush cleaning is required to remove any particles from the cleaned surfaces.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US824382 | 1977-08-15 | ||
| US05/824,382 US4116714A (en) | 1977-08-15 | 1977-08-15 | Post-polishing semiconductor surface cleaning process |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0000701A2 true EP0000701A2 (en) | 1979-02-21 |
| EP0000701A3 EP0000701A3 (en) | 1979-03-07 |
| EP0000701B1 EP0000701B1 (en) | 1981-09-16 |
Family
ID=25241258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100336A Expired EP0000701B1 (en) | 1977-08-15 | 1978-07-10 | Process for the removal of silicon dioxide residue from a semiconductor surface |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4116714A (en) |
| EP (1) | EP0000701B1 (en) |
| JP (1) | JPS5432262A (en) |
| DE (1) | DE2861075D1 (en) |
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| US5896870A (en) * | 1997-03-11 | 1999-04-27 | International Business Machines Corporation | Method of removing slurry particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1335652A (en) * | 1962-07-13 | 1963-08-23 | Cleaning agent for rusted or carbon coated metal surfaces | |
| DE1614103A1 (en) * | 1967-12-06 | 1970-05-06 | Licentia Gmbh | Method for stabilizing diffused silicon rectifiers write |
| US3715249A (en) * | 1971-09-03 | 1973-02-06 | Bell Telephone Labor Inc | Etching si3n4 |
| US3728267A (en) * | 1970-01-14 | 1973-04-17 | Mitsubishi Heavy Ind Ltd | Peeling type pickling compositions |
| US3728154A (en) * | 1970-09-14 | 1973-04-17 | Maagdenberg R | Semiconductor wafer cleaning |
| DE2706519A1 (en) * | 1976-03-25 | 1977-10-06 | Ibm | METHOD OF CLEANING THE SURFACE OF POLISHED SILICON PLATES |
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|---|---|---|---|---|
| DE966879C (en) * | 1953-02-21 | 1957-09-12 | Standard Elektrik Ag | Process for cleaning and / or removal of semiconductor material, in particular germanium and silicon substances |
| GB1423448A (en) * | 1973-07-18 | 1976-02-04 | Plessey Co Ltd | Method of selectively etching silicon nitride |
-
1977
- 1977-08-15 US US05/824,382 patent/US4116714A/en not_active Expired - Lifetime
-
1978
- 1978-07-10 DE DE7878100336T patent/DE2861075D1/en not_active Expired
- 1978-07-10 EP EP78100336A patent/EP0000701B1/en not_active Expired
- 1978-07-12 JP JP8410178A patent/JPS5432262A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1335652A (en) * | 1962-07-13 | 1963-08-23 | Cleaning agent for rusted or carbon coated metal surfaces | |
| DE1614103A1 (en) * | 1967-12-06 | 1970-05-06 | Licentia Gmbh | Method for stabilizing diffused silicon rectifiers write |
| US3728267A (en) * | 1970-01-14 | 1973-04-17 | Mitsubishi Heavy Ind Ltd | Peeling type pickling compositions |
| US3728154A (en) * | 1970-09-14 | 1973-04-17 | Maagdenberg R | Semiconductor wafer cleaning |
| US3715249A (en) * | 1971-09-03 | 1973-02-06 | Bell Telephone Labor Inc | Etching si3n4 |
| DE2706519A1 (en) * | 1976-03-25 | 1977-10-06 | Ibm | METHOD OF CLEANING THE SURFACE OF POLISHED SILICON PLATES |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 83, no. 12, September 22, 1975, Columbus, Ohio, E.G. ZAUGOLNIKOVA: "Effect of the composition of materials for cleaning the surface of silicon on the properties of silicondioxide", abstract no. 107036g, page 643; & Nauchn. Tr. Tashk. Gos. Univ., vol. 447, 1973, Seiten 77-81 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0000701A3 (en) | 1979-03-07 |
| EP0000701B1 (en) | 1981-09-16 |
| US4116714A (en) | 1978-09-26 |
| JPS5432262A (en) | 1979-03-09 |
| DE2861075D1 (en) | 1981-12-03 |
| JPS6214938B2 (en) | 1987-04-04 |
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