TW201326457A - Showerhead for MOCVD apparatus and method of using and manufacturing the same - Google Patents

Abstract

This invention provides a showerhead for an MOCVD apparatus and a method of using and manufacturing the same. The manufacturing method comprises: manufacturing a showerhead body; and forming a regenerative protection layer on the surface of the showerhead body, wherein the regenerative protection layer is used to protect the showerhead body from being etched by the chemical reactive gas and/or plasma during the MOCVD process. The showerhead formed thereby comprises: a showerhead body and a regenerative protection layer on the surface of the showerhead body for protecting the showerhead body. The using method comprises: after the showerhead has been used for a period of time, performing the recycling regeneration on the regenerative material layer to form the recycled protection layer on the regenerative material layer. The embodiment of this invention can effectively protect the showerhead, prolong the service life of the showerhead, and increase the quality of extension layer formed thereby and the utilization rate of the MOCVD apparatus.

Description

Shower head of MOCVD equipment and manufacturing method and using method thereof

The present invention relates to the field of semiconductor technology, and more particularly to a shower head for an MOCVD apparatus, a method of fabricating the same, and a method of using the same.

MOCVD is an abbreviation for Metal-organic Chemical Vapor Deposition. MOCVD is a new type of vapor phase epitaxy technology developed on the basis of vapor phase epitaxy (VPE). It uses organic compounds of group III and II elements and hydrides of group V and VI as crystal growth source materials, and performs vapor phase epitaxy on the substrate by thermal decomposition reaction to grow various III-V groups and II- A thin layer single crystal material of a Group VI compound semiconductor and their multiple solid solution. Generally, the crystal growth in the MOCVD system is carried out in a cold-wall quartz (stainless steel) reaction chamber at normal pressure or low pressure (10-100 Torr), and H2 is used as a carrier gas (Carrier Gas) at a substrate temperature of 500-1200 ° C. The graphite base is heated by radio frequency induction (the substrate is above the graphite base), and H2 is bubbled to carry the metal organic matter to the growth zone through a temperature controlled liquid source.

For details, please refer to the existing MOCVD internal structure diagram shown in FIG. The process chamber 40 has a heated graphite susceptor 20 on which a plurality of wafers 30 to be processed are placed, a shower head (SH) 10 and the heated graphite susceptor 20 and the crystal to be treated. The sprinkler head 10 is made of a material such as stainless steel. The sprinkler head 10 has a plurality of holes therein, and the shower head 10 sprays a gaseous substance on the wafer 30 to be processed through the cavity. A chemical reaction is generated above the wafer 30 to be processed, and a formed reaction substance is deposited on the processing wafer 30 to form an epitaxial layer.

Further information on existing MOCVD equipment can be found in U.S. Patent Application Serial No. US20050136188.

SUMMARY OF THE INVENTION The present invention provides a shower head for an MOCVD apparatus, a method of fabricating the same, and a method of using the same, for improving the quality of an epitaxial layer formed by an MOCVD apparatus, and improving the utilization of the MOCVD apparatus.

In order to solve the problems of the prior art, the technical means adopted by the present invention is to provide a method for manufacturing a shower head of an MOCVD apparatus, comprising: fabricating a shower head body; forming a reproducible protective layer on a surface of the shower head body, The regenerable protective layer serves to protect the showerhead body from etching of chemical reaction gases and/or plasma during MOCVD.

Preferably, the method for manufacturing the reproducible protective layer comprises: forming a layer of a reproducible material on the surface of the shower head; the thickness of the recyclable material layer ranges from 0.005 to 150 mm.

Performing an initial regeneration operation on the recyclable material layer to form an initial protective layer, the initial protective layer and the recyclable material layer constituting the reproducible protective layer, the initial protective layer having a thickness ranging from 0.001 to 30 mm .

Preferably, the material of the renewable material layer is an alloy material or a ceramic material, and the alloy material includes one or more of Y, Er, Rh, and Ir, and the ceramic material includes one of Y2O3, Er2O3, and YF3. Or a variety.

Preferably, the initial regeneration operation comprises: heating the layer of renewable material, and introducing a regeneration gas while heating, the regeneration gas is combined with the layer of renewable material to form an initial protective layer; or Heating the layer of renewable material At the same time, a regenerative plasma is introduced into the surface of the regenerable material layer, and the regenerated plasma is combined with the recyclable material layer to form an initial protective layer; or a regenerative plasma is introduced into the surface of the regenerable material layer. The regenerative plasma is combined with the layer of renewable material to form an initial protective layer.

Preferably, the regeneration gas is one of oxygen or fluorine gas or a combination of the two; the regeneration plasma is a combination of one or both of oxygen ions and fluoride ions, and the heating temperature ranges from 50 to 1200. Celsius.

Preferably, the layer of renewable material is fabricated by welding, electroplating, rolling, rolling, sputtering or deposition processes to combine the layer of recycled material with the body of the showerhead.

Accordingly, the present invention also provides a shower head of an MOCVD apparatus, comprising: a shower head body; a reproducible protective layer on an outer surface of the shower head body, the regenerable protective layer for protecting the shower The head body is free of etching of chemical reaction gases and/or plasma during MOCVD.

Preferably, the reproducible protective layer comprises: a layer of renewable material located on a surface of the shower head body; the layer of the recyclable material may have a thickness of 0.005-150 mm; an initial protective layer located at the And a surface of the regenerated material layer, the initial protective layer and the recyclable material layer constitute the reproducible protective layer; the initial protective layer may have a thickness of 0.001 to 30 mm.

Preferably, the material of the renewable material layer is an alloy material or a ceramic material, and the alloy material includes one or more of Y, Er, Rh, and Ir, and the ceramic material includes one of Y2O3, Er2O3, and YF3. Or a plurality of; the material of the initial protective layer is the layer of the renewable material Combination with oxygen and/or fluorine.

Correspondingly, the present invention also provides a method of using a shower head of an MOCVD apparatus manufactured by the method, after the shower head is used for a period of time, regenerating the layer of the recyclable material, A surface protective layer is formed on the surface of the recycled material layer; the thickness of the loop protective layer ranges from 0.001 to 15 mm.

Preferably, the loop regeneration comprises: heating the layer of renewable material, and introducing a regeneration gas while heating, the regeneration gas being combined with the layer of renewable material to form a loop protection layer; or Regenerating plasma is introduced into the surface of the regenerable material layer while the heating of the recyclable material layer is performed, and the regenerative plasma is combined with the recyclable material layer to form a loop protective layer; A surface of the regenerable material layer is passed through a regenerative plasma, and the regenerated plasma is combined with the layer of recyclable material to form a loop protective layer.

Preferably, the regeneration gas is one of oxygen or fluorine gas or a combination of the two; the regeneration plasma is a combination of one or both of oxygen ions and fluoride ions, and the heating temperature ranges from 50 to 50. 1200 degrees Celsius.

Preferably, the period of time is less than or equal to a period of use of the initial protective layer or the loop protective layer of the surface of the regenerable protective layer.

Compared with the prior art, the embodiment of the invention has the following advantages: by forming a reproducible protective layer on the surface of the shower head body, the regenerable protective layer is used to protect the shower head body, the regenerative protective layer and the spray There is almost no chemical reaction between the main body of the shower head, the source gas of the MOCVD process, the substance formed by the reaction of the source gas, the acidic ion or the alkaline ion of the chemical cleaning method, and the chemical layer can be formed by the formation of the reproducible protective layer. Clean the sprinkler to prevent the surface of the sprinkler from accumulating The substance affects the growth quality of the epitaxial layer, and also prevents mechanical cleaning of the shower head to reduce the utilization of the MOCVD equipment; since the regenerable protective layer is substantially free from acidic or alkaline ions used in chemical cleaning methods. The reaction occurs, so the regenerative protective layer protects the sprinkler and increases the life of the sprinkler, and the recyclable protective layer can be used in a loop to further increase the life of the sprinkler.

The specific embodiments of the present invention will be further described by the following examples and the accompanying drawings.

The quality of the epitaxial layer formed by the existing MOCVD equipment is not high, and the utilization time of the existing MOCVD equipment is low. According to the inventor's research, the by-products and chemically reacted substances in the sprinklers of the MOCVD equipment are accumulated inside the holes of some sprinklers and outside the sprinklers, especially the sprinklers are close to the heating base. The surface causes clogging of the shower head and the formation of particulate matter on the exterior of the shower head. The particles may peel off and adhere to the surface of the wafer to be treated during a long-term MOCVD process, forming particle contamination and affecting the quality of the epitaxial layer. And the sprinkler head blockage also affects the uniformity of the epitaxial layer and the deposition rate, thereby reducing the utilization of MOCVD equipment.

If the sprinkler of the MOCVD device is cleaned periodically by mechanical means (ie, after each deposition process is completed), the surface of the shower head is brushed and cleaned with a metal brush to remove the accumulated substances on the surface of the shower head and the holes. Thereby the surface of the shower head can be kept relatively clean. However, mechanical cleaning interrupts the continuous production of MOCVD and requires the time spent on MOCVD for production, thereby reducing the utilization of MOCVD equipment.

If in-situ chemical cleaning is used, the surface of the showerhead can be bombarded or etched using a plasma containing acidic or basic ions, but the method will accumulate on the surface of the showerhead. The material is removed while damaging the underlying showerhead. For example, sprinklers made of stainless steel are susceptible to plasma etching involving halogen elements. This plasma etching not only causes the surface of the showerhead to be uneven, but also shortens the life of the showerhead.

The inventors contemplate the formation of a protective substance on the surface of the showerhead that protects the sprinkler, prevents and delays damage to the sprinkler during in-situ chemical cleaning, and that the protective material can be periodically renewed.

Specifically, a method for fabricating a shower head of an MOCVD apparatus proposed by the inventors, see a flow chart of a method for fabricating a shower head of an MOCVD apparatus according to an embodiment of the present invention shown in FIG. 2, the method comprising: step S1, making a shower head body; step S2, forming a reproducible protective layer on the surface of the shower head body, the regenerable protective layer for protecting the shower head body from chemical reaction gases and plasma during MOCVD eclipse.

The technical solution of the present invention will be described in detail below with reference to specific embodiments. In order to better explain the technical solution of the present invention, please refer to the cross-sectional structural diagram of the method for fabricating the shower head of the MOCVD apparatus according to an embodiment of the present invention shown in FIGS. 3 to 4.

First, referring to FIG. 3, the shower head main body 100 is produced. The material of the shower head main body 100 may be stainless steel, aluminum alloy or the like. In this embodiment, the material of the shower head main body 100 is stainless steel of the model SS304. A plurality of holes (not shown) are formed in the shower head main body 100. The manufacturing method of the shower head main body 100 is the same as that of the prior art, and a well-known technique of those skilled in the art will not be described in detail herein.

Then, referring to FIG. 3, a layer of reproducible material 101 is formed on the surface of the shower head body 100, and the layer of recyclable material 101 is used for An initial protective layer is subsequently formed on the surface thereof. The initial protective layer and the layer of renewable material constitute the renewable protective layer. The regenerable material layer 101 does not chemically react with the shower head body 100 and can be used to protect the shower head body 100. The layer of recyclable material 101 can be fabricated by processes such as welding, electroplating, rolling, rolling, sputtering, or deposition to combine the recycled material with the body 100 of the showerhead. As an embodiment, the thickness of the renewable material layer 101 ranges from 0.005 to 150 mm, for example, the thickness of the regenerable material layer 101 ranges from 1 mm, 10 mm, 50 mm, 70 mm or 150 mm; In still another embodiment of the invention, the thickness of the layer of renewable material 101 may also range from 0.005 to 30 mm.

The material of the renewable material layer 101 is one or a combination of metal materials such as Y, Er, Rh, Ir, or the material of the renewable material layer 101 may be an alloy material containing the above metal elements; or The material of the recyclable material layer 101 is a compound such as Y2O3, Er2O, or YF3, or the material of the recyclable material layer 101 may be a ceramic material containing the above compound. As an embodiment, the material of the regenerable material layer 101 is Y, which can react with oxygen or/and fluorine to form a stable protective initial protective layer.

It should be noted that only the recyclable material layer 101 is formed on one surface of the shower head main body 100. In practice, all the sprinkler heads 100 may be subjected to source materials and sources. The contact surface of the substance after the chemical reaction of the substance, the chemically clean acidic ion or the alkaline ion needs to form a layer of the recyclable material to effectively protect the shower head body 100.

Next, referring to FIG. 4, the reproducible material layer 101 is subjected to an initial regeneration operation to form an initial protective layer 102, and the initial protective layer 102 and the recyclable material layer 101 constitute a reproducible protective layer. Said The regenerable protective layer is used to protect the shower head body 100, and when the surface of the shower head is chemically cleaned, the regenerable protective layer does not substantially react with acidic ions or alkaline ions during chemical cleaning, The material does not react with the source gas or the source gas during the MOCVD process, so the regenerable protective layer can effectively protect the shower head body 100 from acid ions or alkaline ions. The surface of the body 100.

As an embodiment, the initial regeneration operation includes: heating the renewable material layer 101, and introducing a regeneration gas while heating, the regeneration gas being combined with the renewable material layer 101 to form an initial protective layer. 102; or heating the regenerable material layer 101, contacting the surface of the regenerable material layer 101 with a regenerative plasma while heating, ions, atoms or gas molecules in the regenerated plasma and the regenerable The material layer 101 is combined to form an initial protective layer 102; or the surface of the regenerable material layer 101 is brought into contact with a regenerative plasma, and ions, atoms or gas molecules in the regenerative plasma are combined with the recyclable material layer 110 to form Initial protective layer 102. As an embodiment, the initial protective layer 102 has a thickness ranging from 0.001 to 30 mm.

As an embodiment, the regeneration gas should be a gas that can react with the surface of the recycled material and can form a protective layer, such as, but not limited to, one of oxygen, fluorine gas, or a combination of both; The heating temperature ranges from 50 to 1200 degrees Celsius for inclusion of, but not limited to, one or a combination of oxygen ions, fluoride ions, or both.

It should be noted that since the MOCVD apparatus cleans the surface of the shower head by chemical plasma or alkaline ions, the MOCVD apparatus already has a plasma generating apparatus, and the regenerated plasma does not need to be in the MOCVD. Extra increase in equipment The plasma generating device is added, but the regenerative plasma can be directly generated by using a plasma generating device already in the MOCVD apparatus.

Although in practice, the shower head body 100 and the regenerable material layer 101 are installed in front of the MOCVD apparatus, it is possible that a surface of the regenerable material layer 101 may form a natural oxide layer due to oxidation of oxygen or the like in the air. The material of the oxide layer is the same as that of the initial protective layer 102 (when the initial protective layer 102 is formed by reacting oxygen with the recyclable material layer 101), but the thickness of the natural oxide layer is thin, which is insufficient for effectively protecting the spray. The head main body 100 cannot satisfy a certain period of use, and therefore, it is necessary to perform an initial regeneration operation after the recyclable material layer 101 is formed. The initial regeneration operation will form the initial protective layer 102 on the surface of all exposed layers of renewable material 101.

Referring to FIG. 4, the shower head of the MOCVD apparatus provided by the present invention comprises: a shower head main body 100, which may be made of stainless steel or an alloy. In this embodiment, the sprinkler body is made of stainless steel of the type SS304; A regenerative protective layer is located on the exterior of the showerhead body for protecting the showerhead body from etching of chemical reaction gases and/or plasma during MOCVD.

As an embodiment, the reproducible protective layer comprises: a layer of renewable material 101 on the surface of the shower head body 100; an initial protective layer 102 on the surface of the layer of renewable material 101, the initial protective layer 102 and the renewable material layer 101 constitute the regenerable protective layer.

As an embodiment, the material of the renewable material layer 101 is One or a combination of metal materials such as Y, Er, Rh, Ir, or the material of the renewable material layer 101 may be an alloy material containing the above metal material; or the material of the renewable material layer 101 is The material of the material such as Y2O3, Er2O3, YF3, or the material of the renewable material layer 101 may be a ceramic material containing the above compound; the material of the initial protective layer 102 is the layer of the renewable material 101 and oxygen, fluorine or A combination of other elements. The initial protective layer 102 is formed by performing an initial reproducing operation on the reproducible material layer 101. For the initial reproducing operation, refer to the manufacturing method of the shower head of the MOCVD device, which will not be described herein. The thickness of the regenerable material layer 101 ranges from 0.005 to 150 mm. The thickness of the initial protective layer 102 ranges from 0.001 to 30 mm.

Although the initial protective layer 102 substantially does not chemically react with a substance formed by a chemical reaction between a source substance and a source substance, or an acidic ion or a basic ion used for chemical plasma cleaning, the device works due to MOCVD. The environment is bad (usually heated for 6 to 9 hours in a high temperature environment of 800 to 1200 degrees Celsius), and frequent use of acidic ions or alkaline ions may damage the initial protective layer 102, and therefore, the initial protective layer 102 is in use for a period of time. After the time, the thickness thereof is reduced. In order to effectively protect the shower head main body 100, the recyclable material layer 101 on the surface of the shower head is recirculated, and a loop protective layer is formed on the surface of the recyclable material layer ( Not shown in the figure).

As an embodiment, the loop regeneration includes: heating the renewable material layer 101, and introducing a regeneration gas while heating, the regeneration gas is combined with the renewable material layer 101 to form loop protection. a layer; or heating the regenerable material layer 101 to bring the surface of the regenerable material layer into contact with a regenerative plasma while heating, ions, atoms and gas in the regenerated plasma a body molecule is combined with the layer of renewable material to form a loop protective layer; or the surface of the layer of renewable material is contacted with a regenerative plasma, ions, atoms and gas molecules in the regenerated plasma and the renewable material The layers are combined to form a loop protective layer. The thickness of the regenerable loop protective layer may be 0.001 to 0.2 mm or more depending on the conditions of use of the shower head and the time of use.

As an embodiment, the regeneration gas should be a gas that can react with the surface of the recycled material and can form a protective layer, such as, but not limited to, one of oxygen, fluorine gas, or a combination of both; The heating temperature ranges from 50 to 1200 degrees Celsius, including but not limited to one or a combination of oxygen ions and fluoride ions, and the thickness of the loop protective layer is 0.001 to 15 mm.

The loop regeneration operation of the present invention may also be performed when the initial protective layer 102 is not completely consumed. At this time, the loop operation is for the regenerable material layer 101 and the remaining initial protective layer 102 simultaneously. It is carried out that the regeneration gas can diffuse through the initial protective layer 102 to the regenerable material layer 101 at a high temperature, and ions or atoms in the plasma can also diffuse through the initial protective layer 102 to the recyclable material layer 101.

The loop regeneration operation can also be repeated, that is, after the loop regeneration operation is performed on the recyclable material layer 101, after the surface loop protection layer is used for a period of time, the thickness of the loop protection layer is chemically cleaned. Acid ions or alkaline ions are reduced by damage, and therefore, the recyclable material layer 101 or the recyclable material layer 101 and the loop protective layer can be re-executed before the loop protective layer is consumed. The loop regeneration operation is described.

It should be noted that the shower head or the initial protective layer or the loop protection layer of the present invention is used for a period of time, and the surface of the reproducible protective layer is initially The period of use of the initial protective layer 102 or the loop protective layer corresponds. Typically the period of time should be less than or equal to the period of use. The period of use is related to the thickness of the initial protective layer 102 or the loop protection layer, and the larger the thickness of the initial protective layer 102 or the loop protection layer, the longer the use period.

In summary, by forming a reproducible protective layer on the surface of the shower head body, the regenerable protective layer is used to protect the shower head body, the regenerative protective layer and the shower head body, the source gas of the MOCVD process, The substance formed by the reaction of the source gas, the acidic ion or the alkaline ion of the chemical plasma cleaning method does not substantially undergo a chemical reaction, and the regenerative protective layer is formed, so that the shower head can be chemically cleaned to prevent the spray. The substance deposited on the surface of the head affects the quality of the epitaxial layer, and it also prevents the mechanical cleaning of the shower head from reducing the utilization of the MOCVD equipment; since the regenerable protective layer does not substantially react with chemically reactive acidic or alkaline ions. The reaction, so the regenerative protective layer can protect the sprinkler, improve the service life of the sprinkler, and the recyclable protective layer can be used in a loop, further improving the service life of the sprinkler.

Although the invention has been disclosed above in the preferred embodiments, the invention is not limited thereto. Any changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be determined by the scope defined by the patent scope.

100‧‧‧Spray head body

101‧‧‧Renewable material layer

102‧‧‧Initial protective layer

10‧‧‧Sprinkler

20‧‧‧heated graphite base

30‧‧‧ Wafer

40‧‧‧Process chamber

1 is a schematic view showing the internal structure of a conventional MOCVD apparatus; FIG. 2 is a flow chart showing a manufacturing method of a shower head of an MOCVD apparatus according to an embodiment of the present invention; and FIGS. 3 to 4 are schematic diagrams of a shower head of an MOCVD apparatus according to an embodiment of the present invention. Schematic diagram of the cross-sectional structure of the manufacturing method.

Claims (13)

A method for manufacturing a shower head of an MOCVD apparatus, comprising: fabricating a shower head body; forming a reproducible protective layer on a surface of the shower head body, the regenerable protective layer for protecting the spray The shower head body is free of etching of chemical reaction gases and/or plasma during MOCVD. The method for fabricating a shower head of an MOCVD apparatus according to claim 1, wherein the method for fabricating the reproducible protective layer comprises: forming a layer of a reproducible material on a surface of the shower head; The thickness of the layer of recycled material ranges from 0.005 to 150 mm. Performing an initial regeneration operation on the recyclable material layer to form an initial protective layer, the initial protective layer and the recyclable material layer forming the reproducible protective layer, the thickness of the initial protective layer The range is 0.001~30 mm. The method for manufacturing a shower head of an MOCVD apparatus according to claim 2, wherein the material of the recyclable material layer is an alloy material or a ceramic material, and the alloy material comprises Y, Er, Rh, and Ir. One or more of the ceramic materials include one or more of Y2O3, Er2O3, and YF3. The method of fabricating a shower head of an MOCVD apparatus according to claim 2, wherein the initial regeneration operation comprises: heating the layer of the recyclable material, and introducing a regeneration gas while heating, Said regeneration gas is combined with said layer of renewable material to form an initial protective layer; or a regenerative plasma is introduced into said surface of said renewable material layer while said heating of said layer of renewable material is performed The regenerative plasma is combined with the layer of recyclable material to form an initial protective layer; or the regenerated plasma is introduced into the surface of the regenerable material layer, the regenerated plasma and the The layers of renewable material combine to form an initial protective layer. The method for fabricating a shower head of an MOCVD apparatus according to claim 4, wherein the regeneration gas is one of oxygen or fluorine gas or a combination of both; and the regeneration plasma is oxygen ion or fluoride ion. One or a combination of the two, the heating temperature ranges from 50 to 1200 degrees Celsius. The method of fabricating a shower head of an MOCVD apparatus according to claim 1, wherein the layer of the recyclable material is produced by using a welding, electroplating, rolling, rolling, sputtering or deposition process, The layer of recycled material is combined with the showerhead body. A shower head of an MOCVD apparatus, comprising: a shower head body; and a regenerable protective layer on an outer surface of the shower head body, the regenerable protective layer for protecting the shower The head body is free of etching of chemical reaction gases and/or plasma during MOCVD. The shower head of the MOCVD apparatus according to claim 7, wherein the reproducible protective layer comprises: a layer of a reproducible material on a surface of the shower head body; the recyclable material layer The thickness may be from 0.005 to 150 mm; an initial protective layer is located on the surface of the layer of recyclable material, and the initial protective layer and the layer of recyclable material constitute the reproducible protective layer; The initial protective layer may have a thickness of 0.001 to 30 mm. The shower head of the MOCVD apparatus according to claim 8, wherein the material of the renewable material layer is an alloy material or a ceramic material, and the alloy material comprises one or more of Y, Er, Rh, and Ir. The ceramic material includes one or more of Y2O3, Er2O3, and YF3; the material of the initial protective layer is a combination of the renewable material layer and an oxygen element and/or a fluorine element. A method of using a shower head of an MOCVD apparatus manufactured by the method of claim 2, wherein after the shower head is used for a period of time, the recyclable material layer is subjected to loop regeneration, The surface of the layer of recyclable material forms a loop protection layer; the thickness of the loop protection layer ranges from 0.001 to 15 mm. The method of use according to claim 10, wherein the loop regeneration comprises: heating the layer of the recyclable material, and introducing a regeneration gas while heating, the regeneration gas and the The layer of recyclable material is combined to form the loop protection layer; or a regenerative plasma is introduced into the surface of the recyclable material layer while the heating of the layer of recyclable material is performed, the regeneration Plasma is combined with the layer of recyclable material to form the loop protective layer; or the regenerated plasma is passed through the surface of the regenerable material layer, the regenerative plasma being combined with the layer of recyclable material Forming the loop protection layer. The method of use according to claim 11, wherein the regeneration gas is one of oxygen or fluorine gas or a combination of both; the regeneration plasma is one or both of oxygen ions and fluoride ions. In combination, the heating temperature ranges from 50 to 1200 degrees Celsius. The method of use of claim 12, wherein the period of time is less than or equal to a period of use of the initial protective layer or the loop protective layer of the surface of the regenerable protective layer.