Heterojunction solar cell

Heterojunction solar cells (HJT), variously known as Silicon heterojunctions (SHJ) or Heterojunction with Intrinsic Thin Layer (HIT),[1] are a family of photovoltaic cell technologies based on a heterojunction formed between semiconductors with dissimilar band gaps. They are a hybrid technology, combining aspects of conventional crystalline solar cells with thin-film solar cells. Silicon heterojunction architecture has the highest cell collection efficiency for commercial-sized silicon solar cells.[2] In 2022–2024, SHJ cells are expected to overtake Aluminium Back surface field (Al-BSF) solar cells in market share to become the second-most adopted commercial solar cell technology after PERx/TOPCon, increasing to nearly 20% by 2032.[3]

An unmetallised heterojunction solar cell precursor. The blue colour arises from the dual-purpose Indium tin oxide anti-reflective coating, which also enhances emitter conduction.
A silicon heterojunction solar cell that has been metallised with screen-printed silver paste undergoing Current–voltage curve characterisation
A SEM image depicting the pyramids and antireflection coating of a heterojunction solar cell

SHJ cells generally consist of an active crystalline silicon absorber substrate passivated by a thin layer of hydrogenated intrinsic amorphous silicon (denoted as a-Si:H) or nanocrystalline silicon (the "buffer layer") and appropriately doped amorphous selective contacts. The buffer layer material and the substrate have different band gaps, forming the heterojunction that is analogous to the p-n junction of traditional solar cells. The high efficiency of heterojunction solar cells is owed mostly to the excellent passivation qualities of such intrinsic buffer layers,[4][5][6][7] particularly with respect to separating the highly recombination-active metallic contacts from the absorber. Although intrinsic buffer layers are effectively non-conductive, charge carriers can tunnel through as the thickness is typically less than 10 nm. It is advantageous for the passivating layer to have a higher band gap in order to minimise parasitic absorption of photons, as absorption coefficient is partially dependent on band gap.

Heterojunction cells are commercially mass-produced and are commonly bifacial. As the thin layers are usually temperature sensitive, heterojunction cells are constrained to a low-temperature manufacturing process.[8][9] This presents challenges for electrode metallisation, as the typical silver paste screen printing method requires firing at up to 800°C;[10] well above the upper tolerance for most buffer layer materials. As a result, the electrodes are composed of a low-temperature silver paste or electroplated copper.

History

The heterojunction structure, and the ability of amorphous silicon layers to effectively passivate crystalline silicon has been well documented since the 1970s.[6][11][12] Heterojunction solar cells using amorphous and crystalline silicon were developed with a conversion efficiency of more than 12% in 1983.[13] Sanyo Electric Co. (now a subsidiary of Panasonic Group) filed several patents pertaining to heterojunction devices including a-Si and μc-Si intrinsic layers in the early 1990s, trademarked "heterojunction with intrinsic thin-layer" (HIT).[14][15] The inclusion of the intrinsic layer significantly increased efficiency over doped a-Si heterojunction solar cells through reduced density of trapping states, and reduced dark tunnelling leakage currents.[16]

Research and development of SHJ solar cells was suppressed until the expiry of Sanyo-issued patents in 2011, allowing various companies to develop SHJ technology for commercialisation.[17][18] In 2014, HIT cells with conversion efficiencies exceeding 25% were developed, which was then the highest for single junction crystalline silicon cells.[19] This record was broken more recently in 2018 by Kaneka corporation, which produced 26.7% efficient large area interdigitated back contact (IBC) SHJ solar cells,[20] and again in 2022 by LONGi with 26.8% efficiency. As of 2023, this is the highest recorded efficiency for monojunction silicon solar cells.[2]

Structure
A cross-sectional schematic of the layers of a typical silicon heterojunction solar cell
An energy band diagram showing energy levels of layers in a typical SHJ solar cell

A typical heterojunction solar cell is composed of a p–i–n–i–n-doped stack of silicon layers; the middle being an n-type crystalline silicon wafer and the others being amorphous thin layers. Then, overlayers of an antireflection coating and metal are used for light and current collection.

Absorber

The substrate, in which electron-hole pairs are formed, is usually n-type monocrystalline silicon doped with phosphorus. In industrial production of SHJ solar cells, high quality n-type Czochralski silicon is required because the low-temperature process cannot provide the benefits of gettering and bulk hydrogenation.[10][21] Photons absorbed outside the substrate do not contribute to photocurrent and constitute losses in quantum efficiency.

Buffer and carrier selection

Intrinsic amorphous silicon is then deposited onto both sides of the substrate using PECVD from a mixture of silane (SiH4) and hydrogen (H2), forming the heterojunction and passivating the surface. The selective contacts are then similarly formed by deposition of the p- and n-type highly doped amorphous silicon layers.[22] Examples of dopant gases include phosphine (PH3) for n-type and trimethylborane (B(CH3)3) or diborane (B2H6) for p-type.[23] Due to its defective nature, doped amorphous silicon (as opposed to intrinsic) cannot provide passivation to crystalline silicon; similarly epitaxial growth of any such a-Si layer causes severe detriment to passivation quality and cell efficiency and must be prevented during deposition.[24]

Anti-reflection coating

The dual purpose antireflection coating (ARC), usually composed of Indium tin oxide (ITO), is then sputtered onto both sides to the thickness required for optimum light capture at the peak of the solar spectrum (around 550 nm  ). The optimum thickness for a single-layer ARC is given by;

where is the layer thickness, is the desired wavelength of minimum reflection and is the material's refractive index.

Depending on the refractive index of the ITO (typically ~0.9),[25] the optimum layer thickness is usually 70-80 nm. Due to thin-film interference, the ITO (a dull grey-black ceramic material) appears a vibrant blue colour at this thickness.

Indium tin oxide is a transparent conducting oxide (TCO) which enhances lateral conductivity of the contact surfaces without significantly impeding light transmission. This is necessary because the amorphous layers have a relatively high resistance despite their high doping levels. Due to the scarcity of indium, alternative TCOs such as aluminium-doped zinc oxide (AZO) are being researched for use in SHJ cells.[26] AZO has a much higher chemical sensitivity than ITO, which presents challenges for certain metallisation methods that require etching, such as nickel seed layer etch-backs.[27]

Through evaporation, a double-antireflection coating of magnesium fluoride (MgF2)[28] or aluminium oxide (Al2O3)[25] may be used to further reduce surface reflections, however this step is not currently employed in industrial production.

Metallisation
A SEM-EDS image of a Cu/Sn-plated heterojunction solar cell. The colours are indicative of elements present.

Heterojunction solar cells are typically metallised (ie. fabrication of the metal contacts) in two distinct methods. Screen-printing of silver paste is common in industry as is with traditional solar cells, with a market share of over 98%.[29] However low-temperature silver paste is required for SHJ cells. These suffer major drawbacks including low grid conductivity and high silver consumption,[30][31] volatile production costs[17] or poor adhesion to the front surface.[9][30] Despite their significantly higher cost,[27] the resistivity of low-temperature silver pastes has been estimated to be 4–6 times higher than standard silver paste.[18] To compensate for lowered conductivity, low-temperature silver pastes also consume more silver than conventional silver pastes,[30] however silver consumption is trending downward as the development of screen-printing technology reduces finger linewidths.[32] An alternative (albeit non-commercialised) method is through electroplating using copper, however this requires selective patterning using an inkjet-printed or photolithographically-derived mask.[31][33] Copper plated directly to the ITO also suffers from adhesion issues. Therefore it is usually necessary to first deposit a thin (~1μm) seed layer of nickel through sputtering or electrodeposition.[27][30][34][35]

Multi-junction

Heterojunction–Perovskite tandem structures have been fabricated, with some research groups reporting a power conversion efficiency exceeding the 29.43% Shockley–Queisser limit for crystalline silicon. This feat has been achieved in both monolithic and 4-terminal cell configurations.[36][37] In such devices, in order to reduce thermalisation losses, the wide bandgap Perovskite top cell absorbs high energy photons whilst the SHJ bottom cell absorbs lower energy photons. In a bifacial configuration, the bottom cell can also accept light from the rear surface.

In 2017, tandem solar cells using a SHJ bottom cell and Group III–V semiconductor top cells were fabricated with power conversion efficiencies of 32.8% and 35.9% for 2- and 3-junction non-monolithic stacks respectively.[38]

Alternative heterojunction materials

Aside from the typical c-Si/a-Si:H structure, various groups have successfully produced passivated contact silicon heterojunction solar cells using novel semiconducting materials, such as between c-Si/SiOx,[23] c-Si/MoOx[39][40] and c-Si/poly-Si or c-Si/SiOx/poly-Si (POLO; polycrystalline silicon on oxide).[41][42] Hybrid inorganic–organic heterojunction solar cells have been produced using n-type silicon coated with polyaniline emeraldine base.[43] Heterojunction solar cells have also been produced on multicrystalline silicon absorber substrates.[44]

Band gap energies of common heterojunction semiconductors
Material Band gap energy; Eg (eV) Notes Reference
c-Si ~1.12 Typical figure measured at 298 K [45]
a-Si:H ~1.7 Compared to c-Si, the wider band gap is attributable mostly to the high (~10% in SHJ solar cells) hydrogen content of amorphous silicon.[46] The band gap energy is affected by the crystalline fraction and hydrogen content of the amorphous network, and is dependent on the method in which the thin film is prepared. A higher ratio of H2:SiH4 during deposition increases the band gap energy.[47] [48]
SiOx:H ~1.4–3.3 Band gap increases as oxygen content increases where . A higher ratio of CO2:SiH4 during deposition increases the band gap energy.[49] [50]
MoOx ~3 [40]

Defect kinetics

Defects are sites at which charge carriers can inadvertently become "trapped", making them more likely to recombine through the Shockley-Read-Hall method (SRH Recombination). They are most likely to exist at interfaces (surface recombination), at crystal grain boundaries and dislocations, or at impurities. To prevent losses in efficiency, defects must be passivated (ie. become chemically and electrically neutral). Generally this occurs through bonding of the defect interface with interstitial hydrogen.

Understanding the behaviour of defects, and how they interact with hydrogen over time and in manufacturing processes, is crucial for maintaining the stability and performance of SHJ solar cells.

Light-induced Degradation

The behaviour of light-sensitive defect passivation in amorphous silicon networks has been a topic of study since the discovery of the Staebler–Wronski effect in 1977.[51] Staebler and Wronski found a gradual decrease in photoconductivity and dark conductivity of amorphous silicon thin films upon exposure to light for several hours. This effect is reversible upon dark annealing at temperatures above 150°C and is a common example of reversible Light-induced Degradation (LID) in hydrogenated amorphous silicon devices. The introduction of new band gap states, causing a decrease in the carrier lifetime, was proposed to be the mechanism behind the degradation. Subsequent studies have explored the role of hydrogen migration and metastable hydrogen-trapping defects in the Staebler–Wronski effect.[52]

Amongst many variables, the kinetics and extent of the Staebler–Wronski effect is dependent on crystallite grain size in the thin film[53] and the light soaking illuminance.[54]

Some amorphous silicon devices can also observe the opposite effect through LID, such as the increase in open-circuit voltage (VOC) observed in amorphous silicon solar cells[55][56] and notably SHJ solar cells[57] upon light soaking. Kobayashi, et al. (2016) proposes that this is due to the shifting of the Fermi level of the intrinsic buffer layer closer to the band edges when in contact with the doped amorphous silicon selective contacts,[57] noting that a similar reversal of the Staebler–Wronski effect was observed by Scuto et al. (2015) when hydrogenated a-Si photovoltaic devices were light-soaked under reverse bias.[58]

Deliberate annealing of heterojunction cells in an industrial post-processing step can improve lifetimes and decrease surface recombination velocity. It has been suggested that thermal annealing causes interstitial hydrogen to diffuse closer to the heterointerface, allowing greater saturation of dangling bond defects.[59] Such a process may be enhanced using illumination during annealing, however this can cause degradation before the improvement in carrier lifetimes is achieved, and thus requires careful optimisation in a commercial setting.[60]

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