Heterojunction Devices Fabricated from Sprayed n-Type Ga2O3, Combined with Sputtered p-Type NiO and Cu2O.

This work reports on the properties of heterojunctions consisting of n-type Ga2O3 layers, deposited using ultrasonic spray pyrolysis at high temperature from water-based solution, combined with p-type NiO and Cu2O counterparts, deposited by radio frequency and reactive, direct-current magnetron sputtering, respectively. After a comprehensive investigation of the properties of the single layers, the fabricated junctions on indium tin oxide (ITO)-coated glass showed high rectification, with an open circuit voltage of 940 mV for Ga2O3/Cu2O and 220 mV for Ga2O3/NiO under simulated solar illumination. This demonstrates in praxis the favorable band alignment between the sprayed Ga2O3 and Cu2O, with small conduction band offset, and the large offsets anticipated for both energy bands in the case of Ga2O3/NiO. Large differences in the ideality factors between the two types of heterojunctions were observed, suggestive of distinctive properties of the heterointerface. Further, it is shown that the interface between the high-temperature-deposited Ga2O3 and the ITO contact does not impede electron transport, opening new possibilities for the design of solar cell and optoelectronic device architectures.

Flexible Transparent Heater Fabricated from Spray-Coated In:ZnO/Ag-NWs/In:ZnO Multilayers on Polyimide Foil.

A flexible transparent heater is presented, based on an all-sprayed composite architecture of indium-doped zinc oxide (IZO) layers that sandwich a network of silver nanowires, on a polyimide-foil substrate. This architecture could be materialized through the development of a low-temperature (240 °C) spray-pyrolysis process for the IZO layers, which is compatible with the thermal stability of the transparent polyimide substrate and allows for the formation of compact and transparent layers, without precipitates. The IZO layers entirely embed the silver nanowires, offering protection against environmental degradation and decreasing the junction resistance of the nanowire network. The resulting transparent heaters have a high mean transmittance of 0.76 (including the substrate) and sheet resistance of 7.5 Ω/sq. A steady-state temperature of ~130 °C is achieved at an applied bias of 3.5 V, with fast heater response times, with a time constant of ~4 s The heater is mechanically stable, reaching or surpassing 100 °C (at 3.5 V), under tensile, respectively, compressive-bending stress. This work shows that high-performance transparent heaters can be fabricated using all-sprayed oxide/silver-nanowire composite coatings, that are compatible with large-scale and low-cost production.

High performance organic light-emitting diodes employing ITO-free and flexible TiO x /Ag/Al:ZnO electrodes.

The broad application of flexible optoelectronic devices is still hampered by the lack of an ITO-free and highly flexible transparent electrode. Dielectric/metal/dielectric (DMD) transparent electrodes are promising candidates to replace ITO, especially in flexible devices due to their mechanical stability to bending, high optical transmittance and low sheet resistance (<6 Ω sq-1). This paper reports on organic light emitting diodes (OLEDs) employing a DMD electrode, specifically TiO x /Ag/Al:ZnO (doped with 2 wt% Al2O3) fabricated by sputter deposition, together with a solution-processed organic polymeric emitting layer. The electrodes were sputtered without substrate heating on rigid glass and flexible polyethylene terephthalate (PET). The results showed that the OLED devices on the DMD electrodes outperform the OLEDs on commercial ITO substrates in terms of maximum luminance as well as current efficacy. Specifically, DMD-based devices achieve up to 30% higher current efficacy on glass and up to 260% higher efficacy on PET, as compared to the ITO-based reference devices. Maximum luminance reaches up to 100 000 cd m-2 for the DMD-based OLEDs on glass and 43 000 cd m-2 for those on PET. This performance is due to the low sheet resistance of the electrodes combined with efficient light outcoupling and shows the potential of DMDs to replace ITO in optoelectronic devices. This outstanding type of optoelectronic device paves the way for the future high throughput production of flexible display and photovoltaic devices.

Gentle plasma process for embedded silver-nanowire flexible transparent electrodes on temperature-sensitive polymer substrates.

The present study investigates processing routes to obtain highly conductive and transparent electrodes of silver nanowires (AgNWs) on flexible polyethylene terephthalate (PET) substrate. The AgNWs are embedded into a UV-curable polymer to reduce the electrode roughness and enhance its stability. For the purpose of device integration, the AgNWs must partially protrude from the polymer, which demands that their embedding is followed by a transfer step from a host substrate to the final substrate. Since the AgNWs require some sort of curing (thermal or plasma) to reduce the electrode sheet resistance, a thermally stable host substrate is generally used. This study shows that both thermally stable polyimide, as well as temperature-sensitive PET can be used as flexible host substrates, combined with a gentle, AgNW plasma curing. This is possible by adjusting the fabrication sequence to accommodate the plasma curing step, depending on the host substrate. As a result, embedded AgNW electrodes, transferred from polyimide-to-PET and from PET-to-PET are obtained, with optical transmittance of ∼80% (including the substrate) and sheet resistance of ∼13 Ω/sq., similar to electrodes transferred from glass-to-glass substrates. The embedded AgNW electrodes on PET show superior performance in bending tests, as compared to indium-tin-oxide electrodes. The introduced approach, involving low-cost flexible substrates, AgNW spray-coating and plasma curing, is compatible with high-throughput, roll-to-roll processing.

Ultrathin sputter-deposited plasmonic silver nanostructures.

In this study, ultrathin silver plasmonic nanostructures are fabricated by sputter deposition on substrates patterned by nanoimprint lithography, without additional lift-off processes. Detailed investigation of silver growth on different substrates results in a structured, defect-free silver film with thickness down to 6 nm, deposited on a thin layer of doped zinc oxide. Variation of the aspect ratio of the nanostructure reduces grain formation at the flanks, allowing for well-separated disk and hole arrays, even though conventional magnetron sputtering is less directional than evaporation. The resulting disk-hole array features high average transmittance in the visible range of 71% and a strong plasmonic dipole resonance in the near-infrared region. It is shown that the ultrathin Ag film exhibits even lower optical losses in the NIR range compared to known bulk optical properties. The presented FDTD simulations agree well with experimental spectra and show that for defect-free, ultrathin Ag nanostructures, bulk optical properties of Ag are sufficient for a reliable simulation-based design.

Nanostructured, ultrathin silver-based transparent electrode with broadband near-infrared plasmonic resonance.

A nanostructured transparent electrode with high average visible transmittance of 76%, low sheet resistance of 7.0 Ω/sq and steep transmittance drop in the near-infrared (NIR) range is investigated by simulations and experiments. The electrode is composed of a nanostructured substrate, on which a trilayer, consisting of an ultrathin 14 nm thick silver film embedded between thin films of TiO2 and Al-doped ZnO, is deposited. Directional silver deposition results in the formation of a disk-hole array without additional lift-off or etching steps. While the trilayer approach enables increased visible transmittance, the transmittance in the NIR regime is decreased by a broadband plasmonic dipole excitation in the disk-hole array. Moreover, a rich mode spectrum of weaker multipole surface plasmon excitations is observed in the nanodisk- and nanohole array. The presented electrode holds great potential for applications in optoelectronic devices, solar control coatings and solar cells.

Multifunctional Nanostructures and Nanopocket Particles Fabricated by Nanoimprint Lithography.

Nanostructured surfaces and nanoparticles are already widely employed in many different fields of research, and there is an ever-growing demand for reliable, reproducible and scalable nanofabrication methods. This is especially valid for multifunctional nanomaterials with physical properties that are tailored for specific applications. Here, we report on the fabrication of two types of nanomaterials. Specifically, we present surfaces comprising a highly uniform array of elliptical pillars as well as nanoparticles with the shape of nanopockets, possessing nano-cavities. The structures are fabricated by nanoimprint lithography, physical and wet-chemical etching and sputter deposition of thin films of various materials to achieve a multifunctional nanomaterial with defined optical and magnetic properties. We show that the nanopockets can be transferred to solution, yielding a nanoparticle dispersion. All fabrication steps are carefully characterized by microscopic and optical methods. Additionally, we show optical simulation results that are in good agreement with the experimentally obtained data. Thus, this versatile method allows to fabricate nanomaterials with specific tailor-made physical properties that can be designed by modelling prior to the actual fabrication process. Finally, we discuss possible application areas of these nanomaterials, which range from biology and medicine to electronics, photovoltaics and photocatalysis.

A Zero-Dimensional Mixed-Anion Hybrid Halogenobismuthate(III) Semiconductor: Structural, Optical, and Photovoltaic Properties.

In this contribution, we present the synthesis and characterization of the mixed-anion halogenobismuthate(III) (CH3NH3)6BiI5.22Cl3.78 (MBIC) as an alternative lead-free perovskite-type semiconductor, and discuss its optical, electronic, and photovoltaic properties in comparison to the methylammonium bismuth iodide (CH3NH3)3Bi2I9 (MBI) compound. The exchange of iodide with chloride during synthesis leads to the formation of an orthorhombic A6BX9-type crystal structure ( Cmma, No. 67) with isolated BiX6 octahedra and methylammonium chloride interlayers. The experimentally found optical indirect band gap of 2.25 eV is in good agreement with the calculated value of 2.50 eV derived from DFT simulations. The valence band maximum and the conduction band minimum were determined to be at -6.2 eV and -4.0 eV vs vacuum. Similar to MBI, thin films of MBIC are composed of microcrystalline platelets. Time-resolved photoluminescence measurements show electron transfer of MBIC to mesoporous TiO2. The photovoltaic behavior of both compounds is compared in solar cells with the following device architecture: glass/ITO/compact TiO2/mesoporous TiO2/MBIC or MBI/spiro-OMeTAD/Au. Despite the zero-dimensional structure of MBIC, a maximum power conversion efficiency of 0.18% and a high fill factor of almost 60% were obtained with this material as absorber layer. When stored under inert conditions, these solar cells show an excellent long-term stability over the investigated period of more than 700 days.

Nanostructured as-deposited indium tin oxide thin films for broadband antireflection and light trapping.

Indium tin oxide (ITO) thin films were sputter-deposited at ambient temperature on a glass-like substrate that was periodically nanostructured by UV nanoimprint lithography. Cross gratings of the corrugated and conformal ITO, with different periods and modulation depths, were tailored to exhibit light trapping or antireflection properties at specific spectral windows by combined optical simulations and experiments. For dense gratings, the light transmission in the 450-850 nm range was enhanced by 8% (absolute) compared to flat ITO films, which is one of the largest performance improvements reported in the literature for nanostructured transparent electrodes. Increasing the grating period shifts the threshold for diffraction coupling to waveguide modes in the visible and near infrared part of the spectrum, resulting in broad light trapping behaviour at wavelengths below this threshold. This work demonstrates a simple processing route at ambient temperature for the fabrication of high-performance transparent electrodes in order to fulfil different device requirements.

High performance and low cost transparent electrodes based on ultrathin Cu layer.

Transparent electrodes based on an ultrathin Cu layer, embedded between two dielectrics, are optimized by simulations and experiments. Different dielectrics are screened in transfer matrix simulations for maximizing the broad-band transmittance. Based on this, sputtered electrodes were developed with the Cu embedded between TiOX-coated glass or PET substrate and an Al-doped ZnO (AZO) top layer. It is found that, for ultrathin Cu layers, increased sputter power fosters island coalescence, leading to superior optical and electrical performance compared to previously reported Cu-based electrodes. Simulations showed that the electrode design optimized with air as ambient medium has to be adapted in the case of electrode implementation in a hybrid perovskite solar cell of inverted architecture.

Combined androgen blockade therapy can convert RT-PCR detection of prostate-specific antigen (PSA) and prostate-specific membrane antigen (PSMA) transcripts from positive to negative in the peripheral blood of patients with clinically localized prostate cancer and increase biochemical failure-free survival after curative therapy.

BACKGROUND: The clinical relevance of positive molecular staging as defined by reverse transcriptase-polymerase chain reaction (RT-PCR) detections of both prostate-specific antigen (PSA) and prostate-specific membrane antigen (PSMA) transcripts in the peripheral blood (PB) of patients with prostate cancer is still debatable. METHODS: We analyzed the biochemical failure-free survival (bFFS) of prostate cancer patients with positive molecular staging who underwent immediate curative therapy (Group I, n=39) compared to prostate cancer patients who did convert their positive molecular staging by the administration of combined androgen blockade (CAB) for 12 months prior to curative treatment (Group II, n=15). RESULTS: The median bFFS for Group I was 9 months (95% CI 5-13 months) and was significantly lower compared to Group II (>36 months, p<0.001). In Group I, the median time for PSA values of >2.0 ng/mL was 18 months (95% CI 12-21 months, range 12-36 months). Notably, only one patient from Group II reached PSA values>2.0 ng/mL at 36 months post-curative treatment. CONCLUSIONS: In patients with clinically localized prostate cancer and positive RT-PCR detection of PSA and PSMA transcripts in PB, CAB can convert positive molecular staging status to negative and by doing so it modifies the post-curative therapy bFFS of patients with clinically localized prostate cancer.

Randomized controlled clinical trial of a combination of somatostatin analog and dexamethasone plus zoledronate vs. zoledronate in patients with androgen ablation-refractory prostate cancer.

BACKGROUND: As previously shown, the combination of standard androgen ablation therapy with somatostatin analog and dexamethasone in metastatic androgen ablation-refractory (stage D3) prostate cancer (PrCa) patients has a favorable profile of side-effects, durable objective antitumor activity (up to 60% partial response rate) and palliative effects. Bisphosphonates interfere with bone remodeling at the sites of PrCa bone metastases and have been postulated to have indirect and/or direct anti-PrCa activity. MATERIALS AND METHODS: A randomized controlled clinical trial was conducted to compare a combination of somatostatin analog (octreotide 20 mg i.m. every 28 days) and oral dexamethasone (4 mg daily for 1 month, gradually reduced to 1 mg daily by the fourth month, with a 1 mg daily maintenance dose thereafter) plus zoledronate (4 mg i.v. every 4 weeks) vs. zoledronate only. All patients in both arms remained in basic androgen blockade throughout the study. RESULTS: Thirty-eight stage D3 patients (mean age 72.8 +/- 6.8 years) were randomized to either treatment arm of the study. The trial was stopped after a pre-specified interim analysis met the criteria for early closure, i.e. significant difference in outcomes between the two treatment arms. Partial responses (PR, > or =50% PSA decline) were observed in 13 out of 20 patients with combination therapy vs. none with zoledronate. The combination therapy arm had significantly better outcome with respect to median progression-free survival (7.0 vs. 1.0 months, p < 0.0001), median overall survival (OS) (12.0 vs. 9.0 months, p = 0.0027), median PrCa-specific OS (defined as time from onset of therapy until PrCa-related death) (16 vs. 9.0 months, p = 0.0005) and median duration of bone pain improvement (>14 vs. 4 months p = 0.00001 by log-rank tests). CONCLUSION: For androgen ablation-refractory metastatic PrCa patients under androgen ablation, the combination of dexamethasone, somatostatin analog and zoledronate offered superior objective and palliative clinical responses than zoledronate alone.

Combination therapy using LHRH and somatostatin analogues plus dexamethasone in androgen ablation refractory prostate cancer patients with bone involvement: a bench to bedside approach.

The development of resistance to anticancer therapies is a major hurdle in preventing long-lasting clinical responses to conventional therapies in hormone-refractory prostate cancer. Herein, the molecular evidence documenting that bone metastasis microenvironment survival factors (mainly the paracrine growth hormone-independent, urokinase-type plasminogen activator-mediated increase of IGF-1 and the endocrine production of growth hormone-dependent IGF-1, mainly liver-derived IGF-1 production) produce an epigenetic form of prostate cancer cells that are resistant to proapoptotic therapies is reviewed. Consequently, the authors present the conceptual framework of a novel antibone microenvironment survival factor, mainly an anti-IGF-1 hormonal manipulation for androgen ablation refractory prostate cancer (a combination of conventional androgen ablation therapy [luteinising hormone-releasing hormone agonist-A or orchiectomy]) with dexamethasone plus somatostatin analogue, which yielded durable objective responses and major improvement of bone pain and performance status in stage D3 prostate cancer patients.

Combination of somatostatin analog, dexamethasone, and standard androgen ablation therapy in stage D3 prostate cancer patients with bone metastases.

PURPOSE: Androgen ablation-refractory prostate cancer patients (stage D3) develop painful bone metastases and limited responsiveness to conventional therapies, hence the lack of universally accepted "gold standard" treatment for this poor prognosis clinical setting. We tested the safety and efficacy in stage D3 patients of the combination hormonal therapy, which combines administration of somatostatin analog and dexamethasone with standard androgen ablation monotherapy (luteinizing-hormone releasing-hormone analog or orchiectomy). EXPERIMENTAL DESIGN: Thirty eight patients with stage D3 prostate cancer (mean age 71.8 +/- 5.9 years) continued receiving androgen ablation therapy in combination with oral dexamethasone (4 mg daily for the 1st month of treatment, tapered down to 1 mg daily by the 4th month, with 1 mg daily maintenance dose thereafter) and somatostatin analog (20 mg octreotide i.m. injections every 28 days). RESULTS: Twenty-three of 38 patients (60.5%) receiving this combination regimen had partial responses [PR, >/=50% prostate-specific antigen (PSA) decline], 9 (21.1%) had stable disease, and 7 (18.4%) had progressive disease. In 47.7% (18 of 38) of patients, their serum PSA levels decreased with treatment but did not return to their respective baselines until the end of follow-up (or death from non-prostate cancer-related causes). The median time-to-return to baseline PSA was 12 months (95% CI, 7-17 months), median progression-free survival was 7 months (95% CI, 4.5-9.5 months), median overall survival was 14 months (95% CI, 10.7-17.4 months), and median prostate cancer-specific overall survival (defined as time from onset of combination therapy until prostate cancer-related death) was 16.0 months (95% CI, 11.9-20.1 months). All patients reported significant and durable improvement of bone pain and performance status (for a median duration of 14 months; 95% CI, 9-19 months), without major treatment-related side effects. We observed a statistically significant (P < 0.01) reduction in serum insulin-like growth factor-1 levels at response to the combination therapy. T levels remained suppressed within castration levels at baseline and throughout therapy, including relapse. CONCLUSION: The combination therapy of dexamethasone plus somatostatin analog and standard androgen ablation manipulation produces objective clinical responses and symptomatic improvement in androgen ablation-refractory refractory prostate cancer patients.

Combination of dexamethasone and a somatostatin analogue in the treatment of advanced prostate cancer.

The local microenvironment at the sites of cancer metastases protects tumour cells from anticancer drug-induced apoptosis via mechanisms, such as soluble growth factors and cytokines. The concept of antisurvival factor (ASF) therapy as a component of anticancer treatments aims at neutralising the protective effect conferred upon cancer cells by the survival factor(s) derived by the local microenvironment, in order to enhance the sensitivity and/or reverse the resistance of tumour cells to other anticancer therapeutic strategies. Herein, we review the translation of this concept from ex vivo studies to clinical applications in the setting of prostate cancer refractory to androgen ablation (stage D3). At this stage, which predominantly involves bone metastases, insulin-like growth factor 1 (IGF-1) production (either growth hormone (GH)-dependent or GH-independent) can protect tumour cells from apoptosis, despite the significant suppression of androgens. The application of the ASF therapeutic concept involves the combination of dexamethasone (which suppresses GH-independent IGF-1) and somatostatin analogue (which suppresses endocrine, GH-dependent IGF-1) with the pro-apoptotic effect of the testicular androgen suppression by sustained use of LHRH analogues. In stage D3, patients who had failed anti-androgen withdrawal, chemotherapy and also had several other adverse prognostic features, the ASF-based combination achieved durable objective responses and major symptomatic improvement, paving the way for future applications of this approach. The ASF-based combination therapy illustrates a novel paradigm in cancer treatment: anti-tumour treatment strategies may not only aim at directly inducing cancer cell apoptosis, but can also target the tumour microenvironment and neutralise the protection it confers on metastatic cancer cells. The favourable toxicity profile of this therapeutic approach calls for its testing in a randomised controlled setting in metastatic prostate cancer and, conceivably, in other IGF-1-responsive malignancies.