CN103132084A - Preparation method of high refractive index semiconductor surface anti-reflection passivation composite structure - Google Patents
Preparation method of high refractive index semiconductor surface anti-reflection passivation composite structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a high refractive index semiconductor surface anti-reflection passivation composite structure. The method comprises: I, a layer of dielectric film used for a passivated surface is prepared on the surface of a semiconductor; and II, a dielectric layer with gradual refractive index based on dielectric materials with a high refractive index is prepared on the dielectric film, dielectric materials materials with high refractive index select one type or several types from SiN, HfO2, TiO2, ZrO2, Ta2O5 and Y203according to semiconductor materials which need to be matched and the wavelength range of needed anti-reflection, and an anti-reflection passivation composite structure is combined by the dielectric film and the dielectric layer with the gradual refractive index. According to the preparation method, non-radiative recombination on the surface of the semiconductor is reduced, reflection loss is reduced, charge collection efficiency is effectively improved, and the function of wide spectrum wide angle anti-reflection is achieved.
Description
Technical field
The present invention relates to a kind of preparation method of semiconductor surface deielectric-coating of gradually changed refractive index, in particular, relate to a kind of preparation method of the high-index semiconductor surface reduced passivation resisting composite structure that is applicable to solar cell, belong to micro-nano photon technology field.
Background technology
Boundary reflection rate between the different refractivity material is to affect the important parameter that receives light, sends light and transmission light device and equipment performance, and extremely low boundary reflection rate is the important indicator that pursue in the fields such as light display is shown, wide spectrum light source, solar cell, lens.Usually, adopt the method for evaporation optics antireflective film to reduce the optical interface reflection.In order to reduce the boundary reflection rate in wide-angle wide range scope as far as possible, usually need the blooming of design evaporation multilayer, and optical film material is unique not to the utmost.Complicated film structure not only makes the processing requirement of plated film own improve, and success ratio reduces; In use inevitably also to stand temperature, humidity changes even mechanical shock, optical interface by the blooming evaporation bi-material of multiple layers of different materials, difference due to the thermal expansivity between differing materials, coefficient of wetness and Young's modulus, inevitably can cause the variation of film material specific refractory power, thickness, cause even badly the part blooming to come off, any variation, the capital causes thoroughly destroying even based on the decline of the blooming transmitance of relevant principle, thereby greatly affects the performance of corresponding device and equipment.
Sub-wavelength grate structure be the cycle less than the surface relief optical grating construction (as shown in Figure 1) of lambda1-wavelength, the specific refractory power of two media and corresponding sub-wavelength grate structure is respectively n
1, n
2, n
3, the grating cycle is L, grating vector
, the input angle of incident light and light wave wave vector in a vacuum is respectively q
1And k, the condition that Zero-order diffractive occurs can be expressed as follows:
... (1), by this formula as can be known, the condition of the incident light generation Zero-order diffractive of specific wavelength not only depends on the input angle of incident light, and depends on the specific refractory power of material and the cycle of grating.When enough hour of the cycle of grating, the grating vector value was enough large, made above-mentioned inequality be no longer dependent on the wave vector of incident light and the size of input angle.That is to say, can obtain Zero-order diffractive in wide wavelength and polarizers of big angle scope, can obtain high antireflective effect, become the utmost point effective means that reduces the boundary reflection rate in wide-angle wide range scope, paid close attention to widely.
But aspect making, really utilize sub-wavelength structure to realize that the antireflective effect in wide-angle wide range scope is also restricted.On the one hand, if directly adopt the etched way of boundary material, according to sub-wavelength Zero-order diffractive principle, can obtain extremely low reflectivity undoubtedly in wide-angle and wide range scope, but the surface after etching can produce a lot of defectives, particularly for nanostructure, specific surface area increases, what surface imperfection was brought is non-radiative compound, the existence of these non-radiative recombination centers causes greatly loss for the photoelectric device, the particularly active photoelectric device that consist of thus, become this kind structure can be really as the lethal factor of optical interface, raising corresponding device performance.Another kind of sub-wavelength structure is in the sub-wavelength nanostructure of original material surface growth graded index, adopts this kind method can not cause undoubtedly the non-radiative compound of surface, brings extra photoelectricity loss.But for the base material (such as semiconductor materials such as Si, GaAs, InP) of high refractive index, deielectric-coating material used all is difficult to reach and this semiconductor refractive index coupling usually.Therefore, still there is larger reflection loss undoubtedly in the interface between high-index material and dielectric material, becomes the physical restriction of utilizing this kind method to realize utmost point antiradar reflectivity.
Summary of the invention
Technical problem to be solved by this invention is, overcome the shortcoming of prior art, a kind of non-radiative compound minimizing of semiconductor surface that makes is provided, effectively improves carrier collection efficient, realize the preparation method of the surperficial reduced passivation resisting composite structure of high-index semiconductor of broad-spectrum wide-angle anti-reflection.
In order to solve above technical problem, the invention provides the preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor, comprise step: I. be used for the deielectric-coating of passive surface at high-index semiconductor surface preparation one deck, described deielectric-coating is SiO
2Film, SiN film, TiO
2Film, Al
2O
3Film, HfO
2A kind of or contain the combined films of more than one compositions in film; II. preparation is based on the gradually changed refractive index medium layer of high refractive index medium material on deielectric-coating again, and the high refractive index semiconductor materials that wherein said high refractive index medium material mates as required and the wavelength region that needs anti-reflection thereof are elected SiN, HfO as
2, TiO
2, ZrO
2, Ta
2O
5And Y
2O
3In one or several, described deielectric-coating and gradually changed refractive index medium layer are combined as the reduced passivation resisting composite structure.
The technical scheme that the present invention further limits is: the method for preparing deielectric-coating in the step I comprises PECVD, thermal evaporation deposition, electron-beam evaporation, any one in magnetron sputtering and ald.Described high-index semiconductor comprises Si at least, Ge, III-V family semi-conductor or III-N family semi-conductor, and the reduced passivation resisting structure composite is surperficial in surface launching/reception N-type semiconductorN opto-electronic device, wherein said surface launching/reception N-type semiconductorN opto-electronic device is solar cell, photodiode, surface-emitting laser or face pick-up probe.
Further, the method for preparing the gradually changed refractive index medium layer in the step II is: adopt sol-gel method on described deielectric-coating, and coprecipitation method, hydrothermal method or oblique angle sedimentation directly form the medium layer of gradually changed refractive index.
Further, the method for preparing the gradually changed refractive index medium layer in the step II is: the deposition metal corresponding with the high refractive index medium material on described deielectric-coating is at least Ti, Zr, Ta or Y, and form the gradually changed refractive index medium layer of high refractive index oxide nanostructure by anodised method.
Further, the method for preparing the gradually changed refractive index medium layer in the step II is: the sediment-filled phase refractive index is the index medium material of high, medium and low distribution successively on described deielectric-coating, forms the Multi-layer composite medium layer of gradually changed refractive index.And, can also further prepare sub-wavelength structure on described Multi-layer composite medium layer.
Further, the method for preparing the gradually changed refractive index medium layer in the step II is: Direct precipitation high refractive index medium material film on described deielectric-coating, and prepare sub-wavelength structure on described high refractive index medium material film.
Further, the described method of sub-wavelength structure for preparing is for adopting electron beam exposure, interference lithography, nano impression, anodic oxidation, the method of one of ball photoetching or metal self-assembly received prepares the sub-wavelength structure template, then adopts dry etching based on this template, and the method for wet etching or anodic oxidation etching is transferred to sub-wavelength structure on the high refractive index medium material.
Further, the method for preparing the gradually changed refractive index medium layer in the step II is: preparation high refractive index medium material film also forms micro nano structure thereon on described deielectric-coating, adopt again LB film or spin-coating method to adhere to the adjustable polystyrene sphere of multilayer hole or silicon oxide bead on micro-nano structure, form the compound medium layer of gradually changed refractive index.
The invention has the beneficial effects as follows: the preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor provided by the invention, semi-conductor is still two dimensional structure on the one hand, semiconductor surface is long-pending not to be increased, surface non-radiative is compound can not increased, according to traditional method, the deielectric-coating passivation is passed through on its surface simultaneously, make the non-radiative compound minimizing of semiconductor surface, effectively improve carrier collection efficient.On the other hand, the graded index structure is made on this deielectric-coating surface, thereby realized the broad-spectrum wide-angle anti-reflection, whole composite structure is realized the reduced passivation resisting double effects, can effectively reduce reflection loss, but not reduce carrier collection efficient, the real efficiency of solar cell that effectively improves.
Description of drawings
Fig. 1 is the wide range anti-reflection that is applicable to the high-index semiconductor surface that makes in embodiment 1 and the compound medium layer structure iron of surface passivation;
Fig. 2 is the wide range anti-reflection that is applicable to the high-index semiconductor surface that makes in embodiment 2 and the compound medium layer structure iron of surface passivation;
Fig. 3 is the wide range anti-reflection that is applicable to the high-index semiconductor surface that makes in embodiment 3 and the compound medium layer structure iron of surface passivation;
Fig. 4 is the wide range anti-reflection that is applicable to the high-index semiconductor surface that makes in embodiment 4 and the compound medium layer structure iron of surface passivation;
Fig. 5 is the wide range anti-reflection that is applicable to the high-index semiconductor surface that makes in embodiment 5 and the compound medium layer structure iron of surface passivation;
Fig. 6 is the wide range anti-reflection that is applicable to the high-index semiconductor surface that makes in embodiment 6 and the compound medium layer structure iron of surface passivation;
Fig. 7 is the surface albedo collection of illustrative plates after Si surface making wide range reduced passivation resisting composite dielectric film;
Fig. 8 is the reflectivity collection of illustrative plates after the surperficial reduced passivation resisting composite dielectric film of GaAs surface making;
Fig. 9 is the I-V curve of measuring after the passivation layer passivation on the Si substrate;
Figure 10 is the I-V curve of measuring after the passivation dielectric film passivation on the GaAs substrate.
Embodiment
The present invention is the defective that overcomes prior art, a kind of compound minimizing of semi-conductor (especially high-index semiconductor) surface non-radiative that makes has been proposed, effectively improve carrier collection efficient, realize the preparation method of the surperficial reduced passivation resisting composite structure of high-index semiconductor of broad-spectrum wide-angle anti-reflection.Its method for making technical characterictic comprises step: I. be used for the deielectric-coating of passive surface at high-index semiconductor surface preparation one deck, described deielectric-coating is SiO
2Film, SiN film, TiO
2Film, Al
2O
3Film, HfO
2A kind of or contain the combined films of more than one compositions in film; II. preparation is based on the gradually changed refractive index medium layer of high refractive index medium material on deielectric-coating again, and the high refractive index semiconductor materials that wherein said high refractive index medium material mates as required and the wavelength region that needs anti-reflection thereof are elected SiN, HfO as
2, TiO
2, ZrO
2, Ta
2O
5And Y
2O
3In one or several, described deielectric-coating and gradually changed refractive index medium layer are combined into the reduced passivation resisting composite structure.
The preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor that the present embodiment provides, prepared composite structure step as shown in Figure 1 is as follows.
I. be used for the compact medium film 2 of passive surface at high-index semiconductor 1 surface preparation one deck.Wherein said high-index semiconductor comprises Si, Ge, III-V family semi-conductor, III-N family semi-conductor, II-VI family semi-conductor and other high refractive index semiconductor materials, and the reduced passivation resisting composite structure is applied to the surface launching/reception N-type semiconductorN opto-electronic devices such as surface, photodiode (LED) surface, surface-emitting laser, detector of solar cell absorption region.Wherein said solar cell comprises brilliant Si battery, crystallite Si battery, amorphous Si and multijunction cell thereof, copper indium gallium selenide cell, cadmium selenide cell, dye-sensitized cell, organic battery, and gallium arsenic is that indium phosphorus is battery and their two ends or three end string junction batteries, also comprises the mixing multijunction cell that is made of different system batteries.
The method for preparing deielectric-coating comprises PECVD, the thermal evaporation deposition, and electron-beam evaporation, any one in magnetron sputtering and ald, and prepared deielectric-coating is SiO
2Film, SiN film, TiO
2Film, Al
2O
3Film, HfO
2A kind of or contain the combined films of more than one specific examples of such components in film.
II. adopt sol-gel method on described deielectric-coating, coprecipitation method, the methods such as hydrothermal method or oblique angle sedimentation directly form the medium layer of mean refractive index gradual change, and medium comprises SiN, HfO originally as high-index material
2, TiO
2, ZrO
2, Ta
2O
5And Y
2O
3In one or several combinations.In this example, this medium layer is for adopting the high refractive index medium holes gap gradual change nano structure membrane 31 of sol-gel method or coprecipitation method preparation, thereby regulate the mean refractive index of each layer of high refractive index medium by controlling such high refractive index medium holes gap, thereby obtain the transition of specific refractory power from high refractive index medium entity specific refractory power to air refraction, realize the broad-spectrum wide-angle anti-reflection, combine with the passivation dielectric film that makes in the step I, jointly consist of the deielectric-coating 31 that the broad-spectrum wide-angle reduced passivation resisting combines.
By the composite structure that above method obtains, form the gradually changed refractive index from the high refractive index medium material to air, thereby realized broad-spectrum wide-angle anti-reflection function, combine with the deactivation function of front deielectric-coating, realized the reduced passivation resisting of semiconductor surface.
Fig. 7 and Fig. 8 provide respectively the reflectivity situation after semi-conductor Si and the surperficial surperficial wide range reduced passivation resisting composite structure of making of GaAs, can find out, although the specific refractory power of Si and GaAs is all greater than 3, but no matter be at the Si material surface, or at the GaAs material surface, need can to obtain the wide range anti-reflection effect in wavelength region, and by suitable Structure Improvement, in the needs wavelength region, can obtain reflectivity less than 5%.
Fig. 9 and Figure 10 provide respectively the I-V rational curve after semi-conductor Si and the upper deposition of GaAs passivation dielectric film, as can be seen from these figures, after the passivation dielectric film deposition of such high-index semiconductor through satisfying the demand, all can obtain very low leakage current, can be comparable with the semi-conductor passivation effect of routine.
The preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor that the present embodiment provides, prepared composite structure step as shown in Figure 2 is as follows.
I, step I are identical with step I method in embodiment 1.
II, on described deielectric-coating the metal refining titanium, and form the medium TiOx nano structure 32 of gradually changed refractive index by anodised method.Need to prove: the metal that deposits on deielectric-coating can be the metal corresponding with the high refractive index medium material, is at least Ti, Zr, and Ta or Y, titanium and titanium oxide only provide as example herein.
Wherein, metal titanium membrane can adopt the several different methods preparations such as thermal evaporation, electron beam evaporation, magnetron sputtering, ald.
The characteristic of resulting composite structure and function are as described in Example 1.
Embodiment 3
The preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor that the present embodiment provides, prepared composite structure step as shown in Figure 3 is as follows.
I, step I are identical with step I method in embodiment 1.
II, the sediment-filled phase refractive index is the high refractive index medium material of high, medium and low distribution successively on described deielectric-coating, forms the Multi-layer composite medium layer of gradually changed refractive index.In this example, the high refractive index medium material of deposition is respectively zirconium white by the high, medium and low differentiation of relative refractive index successively, silicon nitride and silicon oxide film, the Multi-layer composite medium layer 33 of formation gradually changed refractive index.
Luxuriant deposition medium film 333,332 and 331 on the compact medium film that makes in the step I, wherein 333 refer to the deielectric-coating zirconium white that specific refractory power is the highest, 332 refer to the deielectric-coating silicon nitride that specific refractory power is higher, 331 refer to the deielectric-coating silicon oxide that specific refractory power is minimum, formed thus the gradually changed refractive index structure, regulate the compactness extent of each layer thickness and deposition, can obtain effective anti-reflection function in the broad-spectrum wide-angle scope, combine with the deactivation function of front deielectric-coating, realized the reduced passivation resisting of semiconductor surface.
Wherein, zirconium white, silicon nitride and silicon oxide film can adopt the several different methods preparations such as thermal evaporation, electron beam evaporation, PECVD, magnetron sputtering, ald.
One or several that to deposit each layer dielectric equipment used can be PECVD, electron beam evaporation, thermal evaporation, magnetron sputtering and ald.
The characteristic of resulting composite structure and function are as described in Example 1.
Embodiment 4
The preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor that the present embodiment provides, prepared composite structure step as shown in Figure 4 is as follows.
I, step I are identical with step I method in embodiment 1.
II, deposit successively zirconium white on described deielectric-coating, silicon nitride and silicon oxide film form the Multi-layer composite medium layer of gradually changed refractive index, further preparation sub-wavelength structure on described Multi-layer composite medium layer.
After carrying out the method for the step II in embodiment 3, continue preparation sub-wavelength structure template on the zirconium white that makes and silicon oxide film, and sub-wavelength structure is transferred on zirconium white and silicon oxide film, form the medium layer 34 of the compound sub-wavelength structure of zirconium white silicon oxide.
The sub-wavelength structure medium layer further improves its broad-spectrum wide-angle anti-reflection performance, combines with the passivation dielectric film for preparing in the step I, obtains the dual function of semiconductor surface broad-spectrum wide-angle reduced passivation resisting.
Embodiment 5
The preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor that the present embodiment provides, prepared composite structure step as shown in Figure 5 is as follows.
I, step I are identical with step I method in embodiment 1.
II, on described deielectric-coating Direct precipitation high refractive index medium film, and on the high refractive index medium film the described sub-wavelength structure of preparation, form the medium layer 35 of gradually changed refractive index.
Adopt the methods such as electron beam evaporation, magnetron sputtering or ald directly to prepare the high refractive index medium film on the compact medium film that makes in the step I, then prepare the sub-wavelength structure template on this high refractive index medium film, the method of utilizing dry etching or wet etching to the high refractive index medium film, forms the high refractive index medium sub-wavelength structure of gradually changed refractive index with described sub-wavelength structure template transfer.
Wherein, the preparation method of high refractive index film is thermal evaporation, PECVD, magnetron sputtering, ald.
The preparation method of sub-wavelength structure template is: electron beam (ionic fluid) is directly write, interference lithography, anodic oxidation, receive ball photoetching, metal self-assembly, nano impression;
Be the multiple etching apparatuss such as reactive ion etching, inductively coupled plasma etching, electron cyclotron resonance etching with the sub-wavelength structure template transfer to the equipment on the high refractive index medium film.
Embodiment 6
The preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor that the present embodiment provides, prepared composite structure step as shown in Figure 6 is as follows.
I, step I are identical with step I method in embodiment 1.
II, on described deielectric-coating preparation high refractive index medium film and form micro nano structure thereon, adopt again LB film or spin-coating method to adhere to the adjustable polystyrene sphere of multilayer hole or silicon oxide bead on micro nano structure, form the compound medium layer of gradually changed refractive index.
Deposition high refractive index medium film and the higher deielectric-coating (as silicon nitride) of specific refractory power on the compact medium film 2 that makes in the step I, consist of the micro nano structure template on the higher deielectric-coating silicon nitride of specific refractory power, and this micro nano structure template is further transferred on above-mentioned high refractive index medium film; Then further prepare multilayer silicon oxide or polystyrene sphere 36 formation multilayer dielectric structures on this high refractive index lamination micro-nano structure, form the medium layer of gradually changed refractive index.
The medium layer of above method preparation by adjusting space and the density between each layer bead, is realized the continuous transition of specific refractory power from silicon oxide (polystyrene sphere) to air, thereby is obtained good broad-spectrum wide-angle anti-reflection performance.Combine with each layer dielectric of front, realize together wide range anti-reflection and the well passivated function of semiconductor surface.
Wherein, multilayer silicon oxide or polystyrene sphere 36 can adopt the several different methods preparations such as LB film, spin coating, as long as can successfully be paved into the regulatable graded index structure of multilayer hole on deielectric-coating.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (10)
1. the preparation method of high-index semiconductor surface reduced passivation resisting composite structure is characterized in that comprising step:
I. be used for the deielectric-coating of passive surface at high-index semiconductor surface preparation one deck, described deielectric-coating is SiO
2Film, SiN film, TiO
2Film, Al
2O
3Film, HfO
2A kind of or contain the combined films of more than one compositions in film;
II. preparation is based on the gradually changed refractive index medium layer of high refractive index medium material on deielectric-coating again, and the high refractive index semiconductor materials that wherein said high refractive index medium material mates as required and the wavelength region that needs anti-reflection thereof are elected SiN, HfO as
2, TiO
2, ZrO
2, Ta
2O
5And Y
2O
3In one or several, described deielectric-coating and gradually changed refractive index medium layer are combined as the reduced passivation resisting composite structure.
2. the preparation method of a kind of high-index semiconductor according to claim 1 surface reduced passivation resisting composite structure, it is characterized in that the method for preparing deielectric-coating in the step I comprises PECVD, the thermal evaporation deposition, electron-beam evaporation, any one in magnetron sputtering and ald.
3. the preparation method of a kind of high-index semiconductor according to claim 1 surface reduced passivation resisting composite structure, it is characterized in that the method for preparing the gradually changed refractive index medium layer in the step II is: adopt sol-gel method on described deielectric-coating, coprecipitation method, hydrothermal method or oblique angle sedimentation directly form the medium layer of gradually changed refractive index.
4. the preparation method of a kind of high-index semiconductor according to claim 1 surface reduced passivation resisting composite structure, it is characterized in that the method for preparing the gradually changed refractive index medium layer in the step II is: the deposition metal corresponding with the high refractive index medium material on described deielectric-coating, be at least Ti, Zr, Ta or Y, and form the gradually changed refractive index medium layer of high refractive index oxide nanostructure by anodised method.
5. the preparation method of a kind of high-index semiconductor according to claim 1 surface reduced passivation resisting composite structure, it is characterized in that the method for preparing the gradually changed refractive index medium layer in the step II is: the sediment-filled phase refractive index is the index medium material of high, medium and low distribution successively on described deielectric-coating, forms the Multi-layer composite medium layer of gradually changed refractive index.
6. the preparation method of the surperficial reduced passivation resisting composite structure of a kind of high-index semiconductor according to claim 5, is characterized in that, further prepares sub-wavelength structure on described Multi-layer composite medium layer.
7. the preparation method of a kind of high-index semiconductor according to claim 1 surface reduced passivation resisting composite structure, it is characterized in that the method for preparing the gradually changed refractive index medium layer in the step II is: Direct precipitation high refractive index medium material film on described deielectric-coating, and prepare sub-wavelength structure on described high refractive index medium material film.
8. the preparation method of according to claim 6 or 7 described a kind of high-index semiconductor surface reduced passivation resisting composite structures, it is characterized in that: the described method of sub-wavelength structure for preparing is for adopting electron beam exposure, interference lithography, nano impression, anodic oxidation, the method of one of ball photoetching or metal self-assembly received prepares the sub-wavelength structure template, then adopts dry etching based on this template, and the method for wet etching or anodic oxidation etching is transferred to sub-wavelength structure on the high refractive index medium material.
9. the preparation method of a kind of high-index semiconductor according to claim 1 surface reduced passivation resisting composite structure, it is characterized in that the method for preparing the gradually changed refractive index medium layer in the step II is: preparation high refractive index medium material film also forms micro nano structure thereon on described deielectric-coating, adopt again LB film or spin-coating method to adhere to the adjustable polystyrene sphere of multilayer hole or silicon oxide bead on micro nano structure, form the compound medium layer of gradually changed refractive index.
10. the preparation method of a kind of high-index semiconductor according to claim 1 surface reduced passivation resisting composite structure, it is characterized in that described in the step I, high-index semiconductor comprises Si at least, Ge, III-V family semi-conductor or III-N family semi-conductor, II-VI family semi-conductor, and the reduced passivation resisting structure composite is surperficial in surface launching/reception N-type semiconductorN opto-electronic device, wherein said surface launching/reception N-type semiconductorN opto-electronic device is solar cell, photodiode, surface-emitting laser or face pick-up probe.
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