The invention relates to a process for the photoelectrochemical etching of semiconductors and to the specific metal-ion treatment of the semiconductors.

Semiconductors are commonly etched for purposes of improving the surface of the semiconductors. Although etching may serve many purposes, there are two primary areas in which etching is useful. First, etching serves to remove "damaged" surface layers from semiconductors. Second, in- "geometrically selective etching", a specific geometric pattern is produced on the semiconductor.

The removal of damaged surface layers by etching is useful in preparing photovoltaic devices in which damaged or less perfect (less than the bulk) surfaces may give rise to undesirable surface states resulting in lowered output parameters, particularly photovoltage and fill factor, and having fewer surface recombination centers, which results primarily in reduced photocurrent. For such uses, the etchant is normally a reagent which attacks the semiconductor chemically, such as by dissolving it or by oxidizing it to form products which are subsequently dissolved at a controlled rate. In this context, particular attention is directed to the exhaustive etching of GaAs crystals disclosed by B.A. Parkinson, A. Heller and B. Miller, Applied Physics Letters 33(6) 521 (1976) by non- convective etching with H₂O_2/H₂SO₄. By using this technique an initially shiny crystal face is converted to a matte non-reflecting surface. As was noted above, this is particularly desireable for photovoltaic applications where matte surfaces reduce light reflection and hence result in higher photocurrents as a result of increased light absorption. Additionally, the treatment of the etched GaAs with ruthenium ions has been shown to increase both the photovoltage and fill factor of a photoelectrochemical cell utilizing the GaAs as a photoanode in a polyselenide electrolyte.

Geometrically selective etching is often radiation induced and, although related to the method of the invention, is performed for a different purpose such as recording holographic data or forming diffraction patterns. Thus, in 1956, A. Uhlir (Bell System Tech. J. 35,33; 1956) first reported electrolytic shaping of Ga and Si by localized illumination to inject carriers in a geometrically controlled fashion and was able to produce a pattern of concentric dimples. In 1966, Yu. V. Pleskov (U.S.S.R. Patent 190,758) selectively cut n-GaAs crystals by photoelectrochemically etching them to obtain a desired surface profile.

Hologram recordings on a polished Si surface were reported by A.L. Delisa et al [Appl. Phys. Letts. 17, 208 (1970)], and were performed by phototoanodically etching the Si surface in a 5% aqueous HF solution. Diffraction patterns on n- and p- crystals and on AlGaAs epitaxial layers, were formed by forming a two beam interference pattern from an HeNe laser onto a semiconductor surface which was etched at the same time with an aqueous solution of an oxidizing agent [L.V. Belyakov et al, Soviet Phys. Tech. Phys. 19, 837 (1974)]. Hologram recordings were effected in CdSe sputtered films on glass by a photoetch process wherein the CdSe film was illuminated by a laser in aqueous HN0₃ or K₃Fe(CN)₆ solution [Sterligov, V.A. and Tygai,V.A., Soviet Tech. Phys. Letts. 1,(1975)J.

Finally, P.D. Greene studied the photoelectrochemical etching of GaAs by Fe⁺³ based etches and found that n-GaAs was etched preferentially compared with p-GaAs and that the rate of etching of n-GaAs depended on the doping concentration [Inst. Phys. Conf. Ser. No. 33A 141 (1977)].

It is, an object of the invention to provide a process for preparing the surface of a semiconductor, particularly a metal chalcogenide, for use as an electrode in a photovoltaic device. According to the process, the metal chalcogenide is immersed in a suitable electrolyte for etching. The electrolyte is selected such that the metal chalcogenide is relatively stable therein in the dark, but unstable under illumination when forming a circuit with a counterelectrode. The metal chalcogenide is electrically connected to an electrode and the electrode is immersed in the electrolyte.

The metal chalcogenide is then illuminated to photoetch the metal chalcogenide thereby improving the surface electronic properties of the chalcogenide and generally providing a matte surface thereon. The intensity of illumination is generally on the order of sunlight.

The above process may be applied to a metal chalcogenide which internally comprises the electrode and wherein the metal chalcogenide is thus automatically electrically connected to the electrode.

Thus, the metal chalcogenide may be in the form of a powder, each particle of which comprises cathodic and anodic sites exposed to said electrolyte.

In one embodiement, the electrolyte used may be a dilute acid; and is preferably selected from the group comprising of H₂SO₄, HC1, HN0₃ and mixtures thereof.

According to one aspect of the invention, at least one of the ions selected from the group consisting of _Ce⁴⁺, _Sn²⁺, _Sn⁴⁺, _Zn²⁺, Cr⁶⁺ or Fe(CN)₆^4-. Fe(CN)₆³- may be added to the electrolyte. As used, the term "ions" is taken to include both the simple and complex forms of the elements having the recited valences. Thus, for example, Cro₄⁼ is included as a complex ion of _Cr6+_.

The metal chalcogenide is preferably selected from the group comprising cadmium, mercury or zinc chalcogenides, alloys of the cadmium, mercury or zinc chalcogenides, and chalcopyrite structured ternary compounds such as CulnS₂ and CulnSe₂. The chalcogenides are most preferably selected from the group consisting of sulfides, selenides, tellurides and mixtures thereof for purposes of the invention.

The invention further relates to the metal chalcogenide electrode and the complete photoelectrochemical system including an electrolyte which may be formed using the above process. The invention likewise relates to the treatment of semiconductors generally by the process.

According to another aspect of the invention, a process for the surface treatment of metal chalcogenides is disclosed. This technique may be used independently of whether a photoelectrochemical etching step is first performed. In this process, a metal chalcogenide is immersed in an aqueous solution of Zn and/or Cr ions. The metal chalcogenide of step a) is then immersed in a solution containing chalcogenide (including polychalcogenide) ions to form the sulfide which remains on the semiconductor.

The process may further include the step of inserting the chalcogenide in a photoelectrochemical cell and connecting the metal chalcogenide as an electrode within the cell. As noted previously, the metal chalcogenide may be etched prior to ion treatment. The invention furhter includes the photoelectrochemical electrode produced by the process.

The concentrations of the etching solution as well as of the ion treatment solution are not critical and may typically range from 0.lM to about 1M.

The invention relates to a process for the photoelectrochemical etching of metal chalcogenide semiconductors as well as to metal ion treatments of such etched semiconductors. The etching according to the invention results in a substantially non-reflecting matte surface. Such a surface is preferred for photovoltaic purposes as it reduces reflection and thus photocurrent losses. Thus, using such a technique may obviate the need for an anti-reflection coating in a solid state photovoltaic cell. In photoelectrochemical cells, where provision'of an anti-reflection coating is normally not feasible, the advantage of such a non-reflecting surface is even more pronounced. When a semiconductor layer which has undergone a process of photoelectrochemical etching according to the invention is used in a photoelectrochemical cell, an increase of all output parameters is noted. Photocurrent typically increases by about 20-25%. This increase is due in part to decreased reflection of the light and also to improved surface electronic properties. Fill factor typically increases by about 10%. Photovoltage change is less predictable, but it too often increases substantially after the photoelectrochemical etch.

It has been further found that the addition of certain metal ions to the photoelectrochemical etching solution often has a beneficial effect on the output parameters of the semiconductor when such semiconductors are used as electrodes in photoelectrochemical cells. Ions which may be used include Ce⁴⁺, _Sn²⁺, _Sn⁴⁺, _Zn²⁺, cr⁶⁺, Fe(CN)₆^4-, and Fe(CN)₆^3-,

Zn and Cr are particularly preferred in that they increase photovoltage when such semiconductors are immersed in a polychalcogenide electrolyte such as is used in photoelectrochemical cells. This treatment may be performed either during photoetching or as a separate subsequent step. This improvement is independent of the above etching treatment.

According to one embodiment of the invention, the semiconductor is in the form of an electrode provided with an electrical contact means. The semiconductor electrode is connected, preferably via an ammeter, to a second inert electrode which may be made of carbon or a metallic material and which is chemically inert towards the electrolyte. The particular second electrode used is of little consequence .(except that it must be substantially chemically inert in the solution and function acceptably as an electrode). The two electrodes are then immersed in an aqueous solution for etching. Although aqueous solutions are preferred, other solutions are possible. The aqueous solution is preferably acidic. Acid concentration is not critical. However, the acid should not be so strong as to chemically attack the semiconductor at an appreciable rate in the dark. As an example, 0.lN H₂SO₄ is suitable for etching many materials. However, other acids, or acidic salts (such as _Cr₀₃ in water) will, depending upon the case, work as well or even better. While acid-solutions have been used, non-acidic solutions which do not fully stabilize the photoelectrodes; i.e., any solution which allows photoelectrochemical corrosion to occur, may also be used. For example, neutral K₃Fe(CN)_6/K₄Fe(CN)₆ solutions have been found to be effective.

The immersed semiconductor is then illuminated to effect etching. While the illumination level itself is not critical, light intensities in the vicinity of sunlight intensity are generally suitable. The photocurrent passing through the semiconductor can be read directly on the ammeter.

Photocurrents through the ammeter will depend upon the illumination intensity as well as upon the emiconductor itself. Generally, illumination levels which give 5-20mA/cm² of photocurrent for a given system are suitable although this range is only given by way of example and large variations outside this range may likewise be used.

In certain systems, the photocurrent will sometimes increase to a maximum and then begin to decrease. In this case, the semiconductor electrode is preferably removed from the electrolyte when such a maximum has been reached.

However, generally, photocurrents begin to decrease immediately upon illumination. In such a system, the extent of photoetching is best established for each system by experiment. As an example, it has been found that for an initial photocurrent density of 10-20mA/cm², illumination for about 5 seconds provides suitable photoetching. Subsequent to etching, the semiconductor surface is then rinsed with water.

Quite obviously, the invention is not limited to the particulars disclosed and alternative embodiments are likewise possible. Thus, a second electrode may be connected directly to the semiconductor electrode without the interposition of an ammeter. In fact, the two electrodes of the system may be constituted by a substrate to which the semiconductor is electrically connected. It is even possible to photoetch using "local cells" existing within the semiconductor itself. Thus, local areas of the semiconductor may act as the counterelectrode. It is further possible to etch a semiconductor powder according to the process of the invention wherein the electrochemical reactions which occur at each electrode during etching of the semiconductor, i.e. oxidation and reduction, occur at different sites on a given particle. In such internally connected embodiments, photocurrent flowing between the electrodes is obviously difficult or impossible to measure.

As a result of photoetching, the semiconductor surface usually becomes matte, i.e., the surface exhibits substantially reduced reflectivity.

According to yet another aspect of the invention, it has been found beneficial to treat semiconductor surfaces with Zn or Cr ions. Although this supplemental ion treatment may be used together with the previous photoetching steps, the ion treatment may likewise be used independently of such an etch to provide improved results.

When using the ion treatment in conjunction with the photoetch process, certain metal ions are added to the electrolyte. The electrolyte may comprise a very dilute acid solution, e.g., in the range of 0.lN. Also, it is preferable in certain instances not to rinse the semiconductor after ion treatment. Such precautions are particularly important if Zn²⁺ ions are used and are critical to a lesser extent for Cr⁶⁺ ions. In other cases, such as when Ce⁴⁺ or Sn²⁺ ions are used, it is preferable to rinse the surface after ion treatment.

Also, even in these instances where no special ion treatment is performed, it may be desirable to rinse the semiconductor to remove chalcogens which form as a result of the etching and which may act as insulators in solid state applications.

i Treatment of semiconductor surfaces by Zn or Cr ions (or their complex ions) is beneficial independent of whether or not a preliminary photoelectrochemical etch is used. In such a process the semiconductor may be dipped into a Cr⁶⁺ ion solution, e.g., K₂CrO₄. ) followed by rinsing. Since rinsing is not always necessary, where not required, such rinsing may be omitted. Immersion of the electrode in a chalcogenide or polychalcogenide electrolyte, such as polysulfide, serves to activate it. Increased voltages typically on the order of about 10% usually result from such treament when the semiconductor is used as a photoelectrode in a polysulfide electrolyte. A similar treatment with Zn²⁺ ions leads to an increase in the photovoltage which may reach on the order of about 20%.

When adding zinc ions (including complex ions), the Zn solution should not be rinsed off completely. If the rinsing step is completely omitted, a white layer of ZnS may remain-on the surface of the semiconductor when it is immersed in a polysulfide solution. This layer may lower output. Thus, in this instance it is preferable to perform a light rinse on the order of about 1-2 drops of water per cm² of semiconductor. Such a rinse usually gives optimum results when a concentrated zinc ion treatment solution (> 1M) of Zn²⁺ is used. The particular material used to provide the Zn ions is not important and Zn salts as well as complex ions all work equally as well.

Although the invention has proven itself particularly effective in electrodes used as photoelectrodes in semiconductor-electrolyte junction systems, the properties which lead to improved "photovoltaic" properties of the semiconductors used as photoelectrodes often cause an improvement in semiconductors used as solid-state photovoltaic devices where the junction is formed with another solid instead of with an electrolyte. Thus, the lowered reflectivity and improved surface electronic properties provided by the process of the invention particularly achieve improved results with electrodes which are to be used in solid-state cells as well as in photoelectrochemical cells. The improved surface electronic properties referred to seem to be related to the reduction of surface recombination of photogenerated charge carriers, although applicants do not wish to be bound by any particular theory.

EXAMPLES

1. CdSe

A layer of CdSe on Cr-plated stainless steel is prepared by coating a pre-oxidized Cr-plated steel substrate with a CdSe paste. The coated substrate is then sintered (see European Application 803002711.9).

This layer is etched for five seconds in 3% Br/ethanol. When tested in a photoelectrochemical cell having an electrolyte 1M in each of KOH, Na₂S and S, the cell gives a short circuit current (S.C.C.) of 6.7 mA, an open circuit voltage (O.C.V.) of 631 mV, and a maximum power voltage (P_max) of 423 mV over 90 ohms using an electrode having an exposed surface area of 0.9 cm² in 0.93 AMI simulated sunlight. This corresponds to 1.99 mW, or 2.3% conversion efficiency with a fill factor of 0.47.

By way of comparison, the CdSe electrode is then connected externally to a carbon rod and both electrodes are immersed in a 2.5% aqueous solution of HN0₃. The CdSe electrode is then illuminated for 5 seconds with the same light intensity as previously. After rinsing, the electrode is again tested, and gives 10 mA S.C.C., 610V O.C.V. and 394 mV over 50 ohms which corresponds to 3.1 mW P_max resulting in a conversion efficiency of 3.6% with a fill factor of 0.51.

2. CdSeo.₆₅Teo.35

A powder composition of CdSe_0.65Te_0.35 is prepared by sintering together a mixture of CdSe and CdTe in a 65/35 molar ratio with CdC1₂. The mixture is applied as a paint with CdCl₂ and nonionic detergent in water to 1 cm² of a Ti substrate which is previously preheated at 650°C for 45 seconds in an argon stream containing about 20 ppm 0₂. The coated substrate is annealed for 12 minutes under the same conditions during which time the CdCl₂ is evaporated. After annealing the coated substrate is etched for 5 seconds in 30% HNO₃ in HC1 solution. The active area is reduced to 0.55 cm² by painting with a solution of tar in trichloroethylene. The resulting layer, when tested under the same conditions as in Example 1, but at 0.85AMl light intensity, gives 6.9 mA S.C.C., 530 mV O.C.V., and 361 mV over a load of 82 ohms. This corresponds to a power of of 1.59mW, a conversion efficiency of 3.4% and a fill factor of 0.44.

By way of comparision, this electrode may then be connected externally 'to a graphite electrode, both electrodes being immersed in a 2M SnCl₂ aqueous solution in 1M HC1 and illuminated by simulated 0.85 AM1 for 30 seconds and then rinsed. The electrode is then immersed for a few seconds in a 0.5M aqueous solution of K₂LrO₄ and patted dry with an absorbant tissue. When tested as previously, the electrode yields 10.3mA S.C.C., 640 mV O.C.V. and 450 mV over 55 ohms. This is a power of 3.68 mW and corresponds to a conversion efficiency of 7.9% with a fill factor of 0.56.

Thus, it is seen that the photoetch treatment results in sharply improved power conversion efficiency and fill factor and short circuit current.

3. CdS

A 1 cm² CdS layer on Ti is prepared by applying a paint of CdS:CdCl₂ (50:3) in an aqueous 5% nonionic detergent to a Ti substrate and is treated and annealed as in Example 2. The layer is etched for 5 seconds in a 1:1 V/V HCl:H₂O solution. When tested as in Example 1, but with an electrolyte containing 1M KOH, 2M Na₂^S and 0.2M S with a light intensity equivalent to 0.5 AMl, the CdS layer gives 1.1 mA S.C.C., 475 mV O.C.V. and 325 mV over 420 ohms. This corresponds to 0.25 mW, 0.48 fill factor, and 0.5% conversion efficiency. This CdS layer is then photoetched as in Example 1, but in an aqueous solution of CrO₃= ions containing 0.5 g CrO₃= in 25 ml H₂O for 15 seconds in 0.5 AMI simulated illumination. The CdS is rinsed, and then tested as before. It then yields 1.43 m S.C.C., 535 mV O.C.V. and 362 mV over 320 ohms. The power is thus 0.41 mW, with a 0.54 fill factor and 0.82% conversion efficiency.

Once again, the photoetching treatment results in greatly improved conversion efficiency.

4. CuInS₂

CuInS₂ is prepared from the elements by heating stoichiometric quantities in an evacuated silica tube at 1150°C for one day. The product is ground, and mixed with 8% InCl₃ in a 5% aqueous nonionic detergent mixture to give a smooth paint. This mixture is applied to a 1 cm² Ti substrate which has been preheated as in Example 3, and annealed under the same conditions as in Example 3, followed by 5 mn. in a 1:2 H₂:Ar atmosphere at 250°C. This layer is marked off to 0.18 cm² with a solution of tar in trichloroethylene, and etched for 5 seconds in 3% HNO₃ in HC1. When tested as in Example 1, under 0.85AMl simulated illumination it gives 194 microamperes S.C.C., 97 mV O.C.V. and 52 mV over 500 ohms. This corresponds to 5.4 microW; 0.29 fill factor and 0.035% conversion efficiency. This layer is photoetched as in Example 1, but in an aqueous solution of O.lM Ce(SO₄)₂ in 0.1M H₂SO₄ for 30 seconds at 0.85 AMI illumination. When tested again, the electrode gives 223 microamperes S.C.C., 103 mV O.C.V., and 55 mV over 400 ohms. This corresponds to 7.56 microwatts, 0.33 fill factor and 0.049% conversion efficiency).

5. CdSe

CdSe is cathodically electroplated from an aqueous acidic electrolyte containing CdS0₄ and SeO₂, onto 1 cm² Ti preheated as in Example 3, and annealed for 10 minutes at 634⁰C in argon containing 20 ppm 0₂ and water vapor. It is then etched for 5 seconds in 3% HN0₃ in HC1. When tested as in Example 1, it yields under 0.95 AMJ. illumination, 7.8 mA S.C.C., 575 mV O.C.V. and 395 mV over 80 ohms. This corresponds to 1.95 mW, 0.43 fill factor and 2.05% conversion efficiency.

The CdSe on the bare Ti substrate is then illuminated (0.95 AM1) in 0.lM K₃Fe(Cn)₆ and 0.5M K₄Fe(CN)₆ in H₂O for 3.0 seconds. The electrode now yields 8.9 mA S.C.C., 580 mV O.C.V. and 398 mV over 65 ohms. This corresponds to 2.44 mW, 0.47 fill factor and 2.57% conversion efficiency.

The CdSe is then immersed for several seconds in 1M aqueous ZnCl₂ solution, and carefully rinsed with one drop of water. The electrode now yields 8.9 mA S.C.C, 635 mV O.C.V. and 410mV over 63 ohms. This corresponds to 2.67 mW, 0.47 fill factor and 2.8% conversion efficiency. An additional dip in a 0.5M aqueous solution of K₂CrO₄, followed by rinsing, increases the O.C.V. to 655 mV, and the conversion efficiency to 2.89%, the other parameters remaining the same.

Although the invention relates particularly to the treatment of metal chalcogenide semiconductors the described treatments may be conducted also on other semiconductor materials such as III-IV compounds, e.g. Gaas.

In that aspect of the invention where a semiconductor is immersed in a solution containing Zn, Cr or a mixture thereof and is then immersed in a solution containing chalcogenide ions this subsequent immersion will result in chalcogenide ions remaining on the semiconductor. The resultant product can then be introduced into a photoelectrochemical cell and connected as an electrode within the cell. The semiconductor may be of a metal chalcogenide and may be made by slurrying with a flux, as described in Application 80302711.9, but the semiconductor may also be made by other methods and may be of other materials, as mentioned above.